Multi-Stage Process and Device Utilizing Structured Catalyst Beds for Production of a Low Sulfur Heavy Marine Fuel Oil

ABSTRACT

A multi-stage process for the distributive production of an ISO 8217 compliant Product Heavy Marine Fuel Oil from ISO 8217 compliant Feedstock Heavy Marine Fuel Oil involving a core process under reactive conditions in a Reaction System composed of one or more reaction vessels, wherein one or more of the reaction vessels contains one or more catalysts in the form of a structured catalyst bed. The Product Heavy Marine Fuel Oil has a sulfur level has a maximum sulfur content (ISO 14596 or ISO 8754) between the range of 0.05 mass % to 1.0 mass. A process plant for conducting the process for conducting the process is disclosed that can utilize the one or more reaction vessels, wherein one or more of the reaction vessels contains one or more catalysts in the form of a structured catalyst bed.

BACKGROUND

There are two basic marine fuel types: distillate based marine fuel,also known as Marine Gas Oil (MGO) or Marine Diesel Oil (MDO); andresidual based marine fuel, also known as heavy marine fuel oil (HMFO).Distillate based marine fuel both MGO and MDO, comprises petroleummiddle distillate fractions separated from crude oil in a refinery via adistillation process. Gasoil (also known as medium diesel) is apetroleum middle distillate in boiling range and viscosity betweenkerosene (light distillate) and lubricating oil (heavy distillate)containing a mixture of C₁₀ to C₁₉ hydrocarbons. Gasoil (a heavydistillate) is used to heat homes and is used blending with lightermiddle distillates as a fuel for heavy equipment such as cranes,bulldozers, generators, bobcats, tractors and combine harvesters.Generally maximizing middle distillate recovery from heavy distillatesmixed with petroleum residues is the most economic use of thesematerials by refiners because they can crack gas oils into valuablegasoline and distillates in a fluid catalytic cracking (FCC) unit.Diesel oils for road use are very similar to gas oils with road usediesel containing predominantly contain a middle distillate mixture ofC₁₀ through C₁₉ hydrocarbons, which include approximately 64% aliphatichydrocarbons, 1-2% olefinic hydrocarbons, and 35% aromatic hydrocarbons.Distillate based marine fuels (MDO and MGO) are essentially road dieselor gas oil fractions blended with up to 15% residual process streams,and optionally up to 5% volume of polycyclic aromatic hydrocarbons(asphaltenes). The residual and asphaltene materials are blended intothe middle distillate to form MDO and MGO as a way to both swell volumeand productively use these low value materials.

Asphaltenes are large and complex polycyclic hydrocarbons with apropensity to form complex and waxy precipitates, especially in thepresence of aliphatic (paraffinic) hydrocarbons that are the primarycomponent of Marine Diesel. Once asphaltenes have precipitated out, theyare notoriously difficult to re-dissolve and are described as fuel tanksludge in the marine shipping industry and marine bunker fuelingindustry. One of skill in the art will appreciate that mixing MarineDiesel with asphaltenes and process residues is limited by thecompatibility of the materials and formation of asphaltene precipitatesand the minimum Cetane number required for such fuels.

Residual based fuels or Heavy Marine Fuel Oil (HMFO) are used by largeocean-going ships as fuel for large two stroke diesel engines for over50 years. HMFO is a blend of the residues generated throughout the crudeoil refinery process. Typical refinery streams combined to from HMFO mayinclude, but are not limited to: atmospheric tower bottoms (i.e.atmospheric residues), vacuum tower bottoms (i.e. vacuum residues)visbreaker residue, FCC Light Cycle Oil (LCO), FCC Heavy Cycle Oil (HCO)also known as FCC bottoms, FCC Slurry Oil, heavy gas oils and delayedcracker oil (DCO), deasphalted oils (DAO); heavy aromatic residues andmixtures of polycylic aromatic hydrocarbons, reclaimed land transportmotor oils; pyrolysis oils and tars; aspahltene solids and tars; andminor portions (often less than 20% vol.) of middle distillate materialssuch as cutter oil, kerosene or diesel to achieve a desired viscosity.HMFO has a higher aromatic content (especially polynuclear aromatics andasphaltenes) than the marine distillate fuels noted above. The HMFOcomponent mixture varies widely depending upon the crude slate (i.e.source of crude oil) processed by a refinery and the processes utilizedwithin that refinery to extract the most value out of a barrel of crudeoil. The HMFO is generally characterized as being highly viscous, highin sulfur and metal content (up to 5 wt %), and high in asphaltenesmaking HMFO the one product of the refining process that hashistorically had a per barrel value less than feedstock crude oil.

Industry statistics indicate that about 90% of the HMFO sold contains3.5 weight % sulfur. With an estimated total worldwide consumption ofHMFO of approximately 300 million tons per year, the annual productionof sulfur dioxide by the shipping industry is estimated to be over 21million tons per year. Emissions from HMFO burning in ships contributesignificantly to both global marine air pollution and local marine airpollution levels.

The International Convention for the Prevention of Pollution from Ships,also known as the MARPOL convention or just MARPOL, as administered bythe International Maritime Organization (IMO) was enacted to preventmarine pollution (i.e. marpol) from ships. In 1997, a new annex wasadded to the MARPOL convention; the Regulations for the Prevention ofAir Pollution from Ships—Annex VI to minimize airborne emissions fromships (SO_(x), NO_(x), ODS, VOC) and their contribution to global airpollution. A revised Annex VI with tightened emissions limits wasadopted in October 2008 and effective 1 Jul. 2010 (hereafter calledAnnex VI (revised) or simply Annex VI).

MARPOL Annex VI (revised) adopted in 2008 established a set of stringentair emissions limits for all vessel and more specifically designatedEmission Control Areas (ECAs). The ECAs under MARPOL Annex VI are: i)Baltic Sea area—as defined in Annex I of MARPOL—SO_(x) only; ii) NorthSea area—as defined in Annex V of MARPOL—SO_(x) only; iii) NorthAmerican—as defined in Appendix VII of Annex VI of MARPOL—SON, NON andPM; and, iv) United States Caribbean Sea area—as defined in Appendix VIIof Annex VI of MARPOL—SON, NON and PM.

Annex VI (revised) was codified in the United States by the Act toPrevent Pollution from Ships (APPS). Under the authority of APPS, theU.S. Environmental Protection Agency (the EPA), in consultation with theUnited States Coast Guard (USCG), promulgated regulations whichincorporate by reference the full text of Annex VI. See 40 C.F.R. §1043.100(a)(1). On Aug. 1, 2012 the maximum sulfur content of all marinefuel oils used onboard ships operating in US waters/ECA was reduced from3.5% wt. to 1.00% wt. (10,000 ppm) and on Jan. 1, 2015 the maximumsulfur content of all marine fuel oils used in the North American ECAwas lowered to 0.10% wt. (1,000 ppm). At the time of implementation, theUnited States government indicated that vessel operators must vigorouslyprepare to comply with the 0.10% wt. (1,000 ppm) US ECA marine fuel oilsulfur standard. To encourage compliance, the EPA and USCG refused toconsider the cost of compliant low sulfur fuel oil to be a valid basisfor claiming that compliant fuel oil was not available for purchase. Forover five years there has been a very strong economic incentive to meetthe marine industry demands for low sulfur HMFO, however technicallyviable solutions have not been realized and a premium price has beencommanded by refiners to supply a low sulfur HMFO compliant with AnnexVI sulfur emissions requirements in the ECA areas.

Since enactment in 2010, the global sulfur cap for HMFO outside of theECA areas was set by Annex VI at 3.50% wt. effective 1 Jan. 2012; with afurther reduction to 0.50% wt, effective 1 Jan. 2020. The global cap onsulfur content in HMFO has been the subject of much discussion in boththe marine shipping and marine fuel bunkering industry. There has beenand continues to be a very strong economic incentive to meet theinternational marine industry demands for low sulfur HMFO (i.e. HMFOwith a sulfur content less than 0.50 wt. %. Notwithstanding this globaldemand, solutions for transforming high sulfur HMFO into low sulfur HMFOhave not been realized or brought to market. There is an on-going andurgent demand for processes and methods for making a low sulfur HMFOcompliant with MARPOL Annex VI emissions requirements.

Replacement of Heavy Marine Fuel Oil with Marine Gas Oil or MarineDiesel:

One primary solution to the demand for low sulfur HMFO to simply replacehigh sulfur HMFO with marine gas oil (MGO) or marine diesel (MDO). Thefirst major difficulty is the constraint in global supply of middledistillate materials that make up 85-90% vol of MGO and MDO. It isreported that the effective spare capacity to produce MGO is less than100 million metric tons per year resulting in an annual shortfall inmarine fuel of over 200 million metric tons per year. Refiners not onlylack the capacity to increase the production of MGO, but they have noeconomic motivation because higher value and higher margins can beobtained from using middle distillate fractions for low sulfur dieselfuel for land-based transportation systems (i.e. trucks, trains, masstransit systems, heavy construction equipment, etc.).

Blending:

Another primary solution is the blending of high sulfur HMFO with lowersulfur containing fuels such as MGO or MDO low sulfur marine diesel(0.1% wt. sulfur) to achieve a Product HMFO with a sulfur content of0.5% wt. In a straight blending approach (based on linear blending)every 1 ton of high sulfur HSFO (3.5% sulfur) requires 7.5 tons of MGOor MDO material with 0.1% wt. S to achieve a sulfur level of 0.5% wt.HMFO. One of skill in the art of fuel blending will immediatelyunderstand that blending hurts key properties of the HMFO, specificallylubricity, fuel density, CCAI, viscosity, flash point and otherimportant physical bulk properties. Blending a mostly paraffinic-typedistillate fuel (MGO or MDO) with a HMFO having a high poly aromaticcontent often correlates with poor solubility of asphaltenes. A blendedfuel is likely to result in the precipitation of asphaltenes and/orwaxing out of highly paraffinic materials from the distillate materialforming an intractable fuel tank sludge. Fuel tank sludge causesclogging of filters and separators, transfer pumps and lines, build-upof sludge in storage tanks, sticking of fuel injection pumps, andplugged fuel nozzles. Such a risk to the primary propulsion system isnot acceptable for a ship in the open ocean.

It should further be noted that blending of HMFO with marine distillateproducts (MGO or MDO) is not economically viable. A blender will betaking a high value product (0.1% S marine gas oil (MGO) or marinediesel (MDO)) and blending it 7.5 to 1 with a low value high sulfur HMFOto create a final IMO/MARPOL compliant HMFO (i.e. 0.5% wt. S Low SulfurHeavy Marine Fuel Oil—LSHMFO) which will sell at a discount to the valueof the principle ingredient (i.e. MGO or MDO).

Processing of Residual Oils.

For the past several decades, the focus of refining industry researchefforts related to the processing of heavy oils (crude oils, distressedoils, or residual oils) has been on upgrading the properties of theselow value refinery process oils to create middle distillate and lighteroils with greater value. The challenge has been that crude oil,distressed oil and residues contain high levels of sulfur, nitrogen,phosphorous, metals (especially vanadium and nickel); asphaltenes andthus exhibit a propensity to form carbon or coke on the catalyst. Thesulfur and nitrogen molecules are highly refractory and aromaticallystable and thus difficult and expensive to crack or remove. Vanadium andnickel porphyrins and other metal organic compounds are responsible forcatalyst contamination and corrosion problems in the refinery. Thesulfur, nitrogen, and phosphorous, must be removed because they arewell-known poisons for the precious metal (platinum and palladium)catalysts utilized in the processes downstream of the atmospheric orvacuum distillation towers.

The difficulties treating atmospheric or vacuum residual streams hasbeen known for many years and has been the subject of considerableresearch and investigation. Numerous residue-oil conversion processeshave been developed in which the goals are same: 1) create a morevaluable, preferably middle distillate range hydrocarbons; and 2)concentrate the contaminates such as sulfur, nitrogen, phosphorous,metals and asphaltenes into a form (coke, heavy coker residue, FCCslurry oil) for removal from the refinery stream. Well known andaccepted practice in the refining industry is to increase the reactionseverity (elevated temperature and pressure) to produce hydrocarbonproducts that are lighter and more purified, increase catalyst lifetimes and remove sulfur, nitrogen, phosphorous, metals and asphaltenesfrom the refinery stream.

In summary, since the announcement of the MARPOL Annex VI standardsreducing the global levels of sulfur in HMFO, refiners of crude oil havehad modest success in their technical efforts to create a process forthe production of a low sulfur substitute for high sulfur HMFO. Despitethe strong governmental and economic incentives and needs of theinternational marine shipping industry, refiners have little economicreason to address the removal of environmental contaminates from highsulfur HMFOs. The global refining industry has been focused upongenerating greater value from each barrel of oil by creating middledistillate hydrocarbons (i.e. diesel) and concentrating theenvironmental contaminates into increasingly lower value streams (i.e.residues) and products (petroleum coke, HMFO). Shipping companies havefocused on short term solutions, such as the installation of scrubbingunits, or adopting the limited use of more expensive low sulfur marinediesel and marine gas oils as a substitute for HMFO. On the open seas,most if not all major shipping companies continue to utilize the mosteconomically viable fuel, that is HMFO. There remains a long standingand unmet need for processes and devices that remove the environmentalcontaminants (i.e. sulfur, nitrogen, phosphorous, metals especiallyvanadium and nickel) from HMFO without altering the qualities andproperties that make HMFO the most economic and practical means ofpowering ocean going vessels.

SUMMARY

It is a general objective to process a high sulfur Feedstock HeavyMarine Fuel Oil (HMFO) in a multi stage process that minimizes thechanges in the desirable properties of the HMFO and minimizes theproduction of by-product hydrocarbons (i.e. light hydrocarbons havingC₁-C₄ and wild naphtha (C₅-C₂₀)) but reduces the sulfur and otherenvironmental contaminates present in the Feedstock HMFO.

A first aspect and illustrative embodiment encompasses a multi-stageprocess for the production of a low sulfur Product Heavy Marine FuelOil, the process involving: mixing a quantity of the Feedstock HeavyMarine Fuel Oil with a quantity of Activating Gas mixture to give aFeedstock Mixture; contacting the Feedstock Mixture with one or morecatalysts in a Reaction System under reactive conditions to form aProcess Mixture from the Feedstock Mixture, wherein said one or morecatalysts are in the form of a structured catalyst bed; receiving theProcess Mixture and separating the Product Heavy Marine Fuel Oil liquidcomponents of the Process Mixture from the gaseous components andby-product hydrocarbon components of the Process Mixture and,discharging the Product Heavy Marine Fuel Oil. In a preferredembodiment, the Reaction System is composed of two or more reactorvessel wherein one or more of the reactor vessels contains a structuredcatalyst bed. In one embodiment, the structured catalyst bed comprises aplurality of catalyst retention structures, each catalyst retentionstructure composed of a pair of fluid permeable corrugated metal sheets,wherein the pair of the fluid permeable corrugated metal sheets arealigned such that the corrugations are out of phase and thereby defininga catalyst rich space and a catalyst lean space within the structuredcatalyst bed, wherein within the catalyst rich space there is one ormore catalyst materials and optionally inert packing materials. Anotheralternative and embodiment the structured catalyst bed contains one ormore catalysts to promote the transformation of the Feedstock mixture toa Process Mixture wherein the structured catalyst bed comprises aplurality of catalyst retention structures, each catalyst retentionstructure composed of a pair of fluid permeable corrugated metal sheets,wherein the pair of the fluid permeable corrugated metal sheets arealigned such that the corrugations are out of phase and thereby defininga catalyst rich space and a catalyst lean space within the structuredcatalyst bed, wherein within the catalyst rich space there is one ormore catalyst materials and optionally inert packing materials.

A second aspect and illustrative embodiment encompasses a device orplant for the production of a Product HMFO. The illustrative devicesembody the above illustrative processes on a commercial scale. Suchdevices include the use of multiple reactor vessels forming a ReactorSystem in which one or more of the reactor vessels contains a structuredcatalyst bed.

A third aspect and illustrative embodiment encompasses a modular reactorcomprising a reaction vessel having an exterior shell that defines aninterior space; one or more inlet piping connections to provide fluidcommunication between a source of feedstock and the interior space ofreaction vessel; one or more outlet piping connections to provide fluidcommunication between the interior of the reaction vessel and productremoval piping; a supporting framework surrounding the reaction vessel,the supporting frame work providing the reaction vessel with structuralsupport, and wherein the supporting framework is truck mountable; andone or more internal structures within the interior space of thereaction vessel. Preferably the internal structures include one or morestructured catalyst beds containing one or more catalyst to promote thetransformation of the Feedstock Mixture to the Process Mixture underreactive conditions. The supporting framework may be dimensioned toconform with the size of an ISO 40 container or ISO 20 foot containerthereby making the modular reactor transportable by truck or rail. Theinternal structures may be removed and replaced either as individualstructures as a whole.

DESCRIPTION OF DRAWINGS

FIG. 1 is a process block flow diagram of an illustrative core processto produce Product HMFO.

FIG. 2 is a process flow diagram of a multistage process fortransforming the Feedstock HMFO and a subsequent core process to produceProduct HMFO.

FIG. 3 is a process flow diagram of a first alternative configurationfor the Reactor System (11) in FIG. 2.

FIG. 4 is a process flow diagram of a second alternative configurationfor the Reactor System (11) in FIG. 2.

FIG. 5 is a side view of a catalyst retention structure component of afirst illustrative embodiment of a structured catalyst bed.

FIG. 6 is a side view of a first illustrative embodiment of a structuredcatalyst bed.

FIG. 7 is a side view of a catalyst retention structure component of asecond illustrative embodiment of a structured catalyst bed.

FIG. 8 is a side view of a second illustrative embodiment of astructured catalyst bed.

DETAILED DESCRIPTION

The inventive concepts as described herein utilize terms that should bewell known to one of skill in the art, however certain terms areutilized having a specific intended meaning and these terms are definedbelow:

Heavy Marine Fuel Oil (HMFO) is a petroleum product fuel compliant withthe ISO 8217 (2017) standards for residual marine fuels except for theconcentration levels of the Environmental Contaminates.

Environmental Contaminates are organic and inorganic components of HMFOthat result in the formation of SO_(x), NO_(x) and particulate materialsupon combustion.

Feedstock HMFO is a petroleum product fuel compliant with the ISO 8217(2017) standards for the physical properties or characteristics of amerchantable HMFO except for the concentration of EnvironmentalContaminates, more specifically the Feedstock HMFO has a sulfur contentgreater than the global MARPOL Annex VI standard of 0.5% wt. sulfur, andpreferably and has a sulfur content (ISO 14596 or ISO 8754) between therange of 5.0% wt. to 1.0% wt.

Product HMFO is a petroleum product fuel compliant with the ISO 8217(2017) standards for the physical properties or characteristics of amerchantable HMFO and has a sulfur content lower than the global MARPOLAnnex VI standard of 0.5% wt. sulfur (ISO 14596 or ISO 8754), andpreferably a maximum sulfur content (ISO 14596 or ISO 8754) between therange of 0.05% wt. to 1.0% wt.

Activating Gas: is a mixture of gases utilized in the process combinedwith the catalyst to remove the environmental contaminates from theFeedstock HMFO.

Fluid communication: is the capability to transfer fluids (eitherliquid, gas or combinations thereof, which might have suspended solids)from a first vessel or location to a second vessel or location, this mayencompass connections made by pipes (also called a line), spools,valves, intermediate holding tanks or surge tanks (also called a drum).

Merchantable quality: is a level of quality for a residual marine fueloil so the fuel is fit for the ordinary purpose it should serve (i.e.serve as a residual fuel source for a marine ship) and can becommercially sold as and is fungible and compatible with other heavy orresidual marine bunker fuels.

Bbl or bbl: is a standard volumetric measure for oil; 1 bbl=0.1589873m³; or 1 bbl=158.9873 liters; or 1 bbl=42.00 US liquid gallons.

Bpd or bpd: is an abbreviation for Bbl per day.

SCF: is an abbreviation for standard cubic foot of a gas; a standardcubic foot (at 14.73 psi and 60° F.) equals 0.0283058557 standard cubicmeters (at 101.325 kPa and 15° C.).

Bulk Properties: are broadly defined as the physical properties orcharacteristics of a merchantable HMFO as required by ISO 8217 (2017);and more specifically the measurements include: kinematic viscosity at50° C. as determined by ISO 3104; density at 15° C. as determined by ISO3675; CCAI value as determined by ISO 8217, ANNEX B; flash point asdetermined by ISO 2719; total sediment—aged as determined by ISO10307-2; carbon residue—micro method as determined by ISO 10370; andalso preferably aluminum plus silicon content as determined by ISO10478.

The inventive concepts are illustrated in more detail in thisdescription referring to the drawings, in which FIG. 1 shows thegeneralized block process flows for a core process of reducing theEnvironmental Contaminates in a Feedstock HMFO and producing a ProductHMFO. A predetermined volume of Feedstock HMFO (2) is mixed with apredetermined quantity of Activating Gas (4) to give a FeedstockMixture. The Feedstock HMFO utilized generally complies with the bulkphysical and certain key chemical properties for a residual marine fueloil otherwise compliant with ISO 8217 (2017) exclusive of theEnvironmental Contaminates. More particularly, when the EnvironmentalContaminate is sulfur, the concentration of sulfur in the Feedstock HMFOmay be between the range of 5.0% wt. to 1.0% wt. The Feedstock HMFOshould have bulk physical properties required of an ISO 8217 (2017)compliant HMFO. The Feedstock HMFO should exhibit the Bulk Propertiesof: a maximum of kinematic viscosity at 50° C. (ISO 3104) between therange from 180 mm²/s to 700 mm²/s; a maximum of density at 15° C. (ISO3675) between the range of 991.0 kg/m³ to 1010.0 kg/m³; a CCAI in therange of 780 to 870; and a flash point (ISO 2719) no lower than 60° C.Properties of the Feedstock HMFO connected to the formation ofparticulate material (PM) include: a total sediment—aged (ISO 10307-2)less than 0.10% wt. and a carbon residue—micro method (ISO 10370) lessthan 20% wt. and preferably a aluminum plus silicon (ISO 10478) contentof less than 60 mg/kg. Environmental Contaminates other than sulfur thatmay be present in the Feedstock HMFO over the ISO requirements mayinclude vanadium, nickel, iron, aluminum and silicon substantiallyreduced by the process of the present invention. However, one of skillin the art will appreciate that the vanadium content serves as a generalindicator of these other Environmental Contaminates. In one preferredembodiment the vanadium content is ISO compliant so the Feedstock HMFOhas a maximum vanadium content (ISO 14597) between the range from 350mg/kg to 450 ppm mg/kg.

As for the properties of the Activating Gas, the Activating Gas shouldbe selected from mixtures of nitrogen, hydrogen, carbon dioxide, gaseouswater, and methane. The mixture of gases within the Activating Gasshould have an ideal gas partial pressure of hydrogen (p_(H2)) greaterthan 90% of the total pressure of the Activating Gas mixture (P) andmore preferably wherein the Activating Gas has an ideal gas partialpressure of hydrogen (p_(H2)) greater than 95% of the total pressure ofthe Activating Gas mixture (P). It will be appreciated by one of skillin the art that the molar content of the Activating Gas is anothercriterion the Activating Gas should have a hydrogen mole fraction in therange between 80% and 100% of the total moles of Activating Gas mixture.

The Feedstock Mixture (i.e. mixture of Feedstock HMFO and ActivatingGas) is brought up to the process reactive conditions of temperature andpressure and introduced into a Reactor System, preferably a reactorvessel, so the Feedstock Mixture is then contacted under reactiveconditions with one or more catalysts (8) to form a Process Mixture fromthe Feedstock Mixture.

The core process reactive conditions are selected so the ratio of thequantity of the Activating Gas to the quantity of Feedstock HMFO is 250scf gas/bbl of Feedstock HMFO to 10,000 scf gas/bbl of Feedstock HMFO;and preferably between 2000 scf gas/bbl of Feedstock HMFO 1 to 5000 scfgas/bbl of Feedstock HMFO more preferably between 2500 scf gas/bbl ofFeedstock HMFO to 4500 scf gas/bbl of Feedstock HMFO. The processconditions are selected so the total pressure in the first vessel isbetween of 250 psig and 3000 psig; preferably between 1000 psig and 2500psig, and more preferably between 1500 psig and 2200 psig. The processreactive conditions are selected so the indicated temperature within thefirst vessel is between of 500° F. to 900° F., preferably between 650°F. and 850° F. and more preferably between 680° F. and 800° F. Theprocess conditions are selected so the liquid hourly space velocitywithin the first vessel is between 0.05 oil/hour/m³ catalyst and 1.0oil/hour/m³ catalyst; preferably between 0.08 oil/hour/m³ catalyst and0.5 oil/hour/m³ catalyst; and more preferably between 0.1 oil/hour/m³catalyst and 0.3 oil/hour/m³ catalyst to achieve deep desulfurizationwith product sulfur levels below 0.1 ppmw.

One of skill in the art will appreciate that the core process reactiveconditions are determined considering the hydraulic capacity of theunit. Exemplary hydraulic capacity for the treatment unit may be between100 bbl of Feedstock HMFO/day and 100,000 bbl of Feedstock HMFO/day,preferably between 1000 bbl of Feedstock HMFO/day and 60,000 bbl ofFeedstock HMFO/day, more preferably between 5,000 bbl of FeedstockHMFO/day and 45,000 bbl of Feedstock HMFO/day, and even more preferablybetween 10,000 bbl of Feedstock HMFO/day and 30,000 bbl of FeedstockHMFO/day.

The transition metal heterogeneous catalyst utilized comprises a porousinorganic oxide catalyst carrier and a transition metal catalytic metal.The porous inorganic oxide catalyst carrier is at least one carrierselected from the group consisting of alumina, alumina/boria carrier, acarrier containing metal-containing aluminosilicate, alumina/phosphoruscarrier, alumina/alkaline earth metal compound carrier, alumina/titaniacarrier and alumina/zirconia carrier. The transition metal catalyticmetal component of the catalyst is one or more metals selected from thegroup consisting of group 6, 8, 9 and 10 of the Periodic Table. In apreferred and illustrative embodiment, the transition metalheterogeneous catalyst is a porous inorganic oxide catalyst carrier anda transition metal catalyst, in which the preferred porous inorganicoxide catalyst carrier is alumina and the preferred transition metalcatalyst is Ni—Mo, Co—Mo, Ni—W or Ni—Co—Mo. The process by which thetransition metal heterogeneous catalyst is manufactured is known in theliterature and preferably the catalysts are commercially available ashydrodemetallization catalysts, transition catalysts, desulfurizationcatalyst and combinations of these which might be pre-sulfided. Asdescribed below, the transition metal heterogeneous catalyst is part ofa structured catalyst bed in which the catalyst particles aredistributed within an otherwise inert supporting structure to achieve anoptimized balance between catalyst activity per unit volume and thelinear space velocity of the Feedstock Mixture. This is described ingreater detail below in relation to the structured catalyst bedconfiguration itself.

The Process Mixture (10) in this core process is removed from theReactor System (8) and from being in contact with the one or morecatalyst and is sent via fluid communication to a second vessel (12),preferably a gas-liquid separator or hot separators and cold separators,for separating the liquid components (14) of the Process Mixture fromthe bulk gaseous components (16) of the Process Mixture. The gaseouscomponents (16) are treated beyond the battery limits of the immediateprocess. Such gaseous components may include a mixture of Activating Gascomponents and lighter hydrocarbons (mostly methane, ethane and propanebut some wild naphtha) that may have been formed as part of theby-product hydrocarbons from the process.

The Liquid Components (16) in this core process are sent via fluidcommunication to a third vessel (18), preferably a fuel oil productstripper system, for separating any residual gaseous components (20) andby-product hydrocarbon components (22) from the Product HMFO (24). Theresidual gaseous components (20) may be a mixture of gases selected fromthe group consisting of: nitrogen, hydrogen, carbon dioxide, hydrogensulfide, gaseous water, C₁-C₅ hydrocarbons. This residual gas is treatedoutside of the battery limits of the immediate process, combined withother gaseous components (16) removed from the Process Mixture (10) inthe second vessel (12). The liquid by-product hydrocarbon component,which are condensable hydrocarbons formed in the process (22) may be amixture selected from the group consisting of C₅-C₂₀ hydrocarbons (wildnaphtha) (naphtha—diesel) and other condensable light liquid (C₃-C₈)hydrocarbons that can be utilized as part of the motor fuel blendingpool or sold as gasoline and diesel blending components on the openmarket. These liquid by-product hydrocarbons should be less than 15%wt., preferably less than 5% wt. and more preferably less than 3% wt. ofthe overall process mass balance.

The Product HMFO (24) resulting from the core process is discharged viafluid communication into storage tanks beyond the battery limits of theimmediate process. The Product HMFO complies with ISO 8217 (2017) andhas a maximum sulfur content (ISO 14596 or ISO 8754) between the rangeof 0.05 mass % to 1.0 mass % preferably a sulfur content (ISO 14596 orISO 8754) between the range of 0.05 mass % ppm and 0.7 mass % and morepreferably a sulfur content (ISO 14596 or ISO 8754) between the range of0.1 mass % and 0.5 mass %. The vanadium content of the Product HMFO isalso ISO compliant with a maximum vanadium content (ISO 14597) betweenthe range from 350 mg/kg to 450 ppm mg/kg, preferably a vanadium content(ISO 14597) between the range of 200 mg/kg and 300 mg/kg and morepreferably a vanadium content (ISO 14597) between the range of 50 mg/kgand 100 mg/kg.

The Product HFMO should have bulk physical properties that are ISO 8217(2017) compliant. The Product HMFO should exhibit Bulk Properties of: amaximum of kinematic viscosity at 50° C. (ISO 3104) between the rangefrom 180 mm²/s to 700 mm²/s; a maximum of density at 15° C. (ISO 3675)between the range of 991.0 kg/m³ to 1010.0 kg/m³; a CCAI value in therange of 780 to 870; a flash point (ISO 2719) no lower than 60.0° C.; atotal sediment—aged (ISO 10307-2) of less than 0.10 mass %; a carbonresidue—micro method (ISO 10370) lower than 20 mass %, and alsopreferably an aluminum plus silicon (ISO 10478) content of less than 60mg/kg.

Relative the Feedstock HMFO, the Product HMFO will have a sulfur content(ISO 14596 or ISO 8754) between 1% and 20% of the maximum sulfur contentof the Feedstock HMFO. That is the sulfur content of the Product will bereduced by about 80% or greater when compared to the Feedstock HMFO.Similarly, the vanadium content (ISO 14597) of the Product HMFO isbetween 1% and 20% of the maximum vanadium content of the FeedstockHMFO. One of skill in the art will appreciate that the above dataindicates a substantial reduction in sulfur and vanadium contentindicate a process having achieved a substantial reduction in theEnvironmental Contaminates from the Feedstock HMFO while maintaining thedesirable properties of an ISO 8217 (2017) compliant and merchantableHMFO.

As a side note, the residual gaseous component is a mixture of gasesselected from the group consisting of: nitrogen, hydrogen, carbondioxide, hydrogen sulfide, gaseous water, C₁-C₅ hydrocarbons. An aminescrubber will effectively remove the hydrogen sulfide content which canthen be processed using technologies and processes well known to one ofskill in the art. In one preferable illustrative embodiment, thehydrogen sulfide is converted into elemental sulfur using the well-knownClaus process. An alternative embodiment utilizes a proprietary processfor conversion of the Hydrogen sulfide to hydrosulfuric acid. Eitherway, the sulfur is removed from entering the environment prior tocombusting the HMFO in a ships engine. The cleaned gas can be vented,flared or more preferably recycled back for use as Activating Gas.

Product HMFO

The Product HFMO resulting from the disclosed illustrative process is ofmerchantable quality for sale and use as a heavy marine fuel oil (alsoknown as a residual marine fuel oil or heavy bunker fuel) and exhibitsthe bulk physical properties required for the Product HMFO to be an ISOcompliant (i.e. ISO 8217 (2017)) residual marine fuel oil. The ProductHMFO should exhibit the Bulk Properties of: a maximum of kinematicviscosity at 50° C. (ISO 3104) between the range from 180 mm²/s to 700mm²/s; a density at 15° C. (ISO 3675) between the range of 991.0 kg/m³to 1010.0 kg/m³; a CCAI is in the range of 780 to 870; a flash point(ISO 2719) no lower than 60° C.; a total sediment—aged (ISO 10307-2)less than 0.10% wt.; and a carbon residue—micro method (ISO 10370) lessthan 20% wt.; and also preferably an aluminum plus silicon (ISO 10478)content no more than of 60 mg/kg.

The Product HMFO has a sulfur content (ISO 14596 or ISO 8754) less than0.5 wt % and preferably less than 0.1% wt. and complies with the IMOAnnex VI (revised) requirements for a low sulfur and preferably anultra-low sulfur HMFO. That is the sulfur content of the Product HMFOhas been reduced by about 80% or greater when compared to the FeedstockHMFO. Similarly, the vanadium content (ISO 14597) of the Product HeavyMarine Fuel Oil is less than 20% and more preferably less than 10% ofthe maximum vanadium content of the Feedstock Heavy Marine Fuel Oil. Oneof skill in the art will appreciate that a substantial reduction insulfur and vanadium content of the Feedstock HMFO indicates a processhaving achieved a substantial reduction in the EnvironmentalContaminates from the Feedstock HMFO; of equal importance is this hasbeen achieved while maintaining the desirable properties of an ISO 8217(2017) compliant HMFO.

The Product HMFO not only complies with ISO 8217 (2017) (and ismerchantable as a residual marine fuel oil or bunker fuel), the ProductHMFO has a maximum sulfur content (ISO 14596 or ISO 8754) between therange of 0.05% wt. to 1.0% wt. preferably a sulfur content (ISO 14596 orISO 8754) between the range of 0.05% wt. ppm and 0.5% wt. and morepreferably a sulfur content (ISO 14596 or ISO 8754) between the range of0.1% wt. and 0.5% wt. The vanadium content of the Product HMFO is wellwithin the maximum vanadium content (ISO 14597) required for an ISO 8217(2017) residual marine fuel oil exhibiting a vanadium content lower than450 ppm mg/kg, preferably a vanadium content (ISO 14597) lower than 300mg/kg and more preferably a vanadium content (ISO 14597) less than 50mg/kg.

One knowledgeable in the art of marine fuel blending, bunker fuelformulations and the fuel requirements for marine shipping fuels willreadily appreciate that without further compositional changes orblending, the Product HMFO can be sold and used as a low sulfur MARPOLAnnex VI compliant heavy (residual) marine fuel oil that is a directsubstitute for the high sulfur heavy (residual) marine fuel oil or heavybunker fuel currently in use. One illustrative embodiment is an ISO 8217(2017) compliant low sulfur heavy marine fuel oil comprising (andpreferably consisting essentially of) hydroprocessed ISO 8217 (2017)compliant high sulfur heavy marine fuel oil, wherein the sulfur levelsof the hydroprocessed ISO 8217 (2017) compliant high sulfur heavy marinefuel oil is greater than 0.5% wt. and wherein the sulfur levels of theISO 8217 (2017) compliant low sulfur heavy marine fuel oil is less than0.5% wt. Another illustrative embodiment is an ISO 8217 (2017) compliantultra-low sulfur heavy marine fuel oil comprising (and preferablyconsisting essentially of) a hydroprocessed ISO 8217 (2017) complianthigh sulfur heavy marine fuel oil, wherein the sulfur levels of thehydroprocessed ISO 8217 (2017) compliant high sulfur heavy marine fueloil is greater than 0.5% wt. and wherein the sulfur levels of the ISO8217 (2017) compliant low sulfur heavy marine fuel oil is less than 0.1%wt.

Because of the present invention, multiple economic and logisticalbenefits to the bunkering and marine shipping industries can berealized. The benefits include minimal changes to the existing heavymarine fuel bunkering infrastructure (storage and transferring systems);minimal changes to shipboard systems are needed to comply with emissionsrequirements of MARPOL Annex VI (revised); no additional training orcertifications for crew members will be needed, amongst the realizablebenefits. Refiners will also realize multiple economic and logisticalbenefits, including: no need to alter or rebalance the refineryoperations, crude slate and product streams to meet a new market demandfor low sulfur or ultralow sulfur HMFO; no additional units are neededin the refinery with additional hydrogen or sulfur capacity because theillustrative process can be conducted as a stand-alone unit; refineryoperations can remain focused on those products that create the greatestvalue from the crude oil received (i.e. production of petrochemicals,gasoline and distillate (diesel); refiners can continue using theexisting slates of crude oils without having to switch to sweeter orlighter crudes to meet the environmental requirements for HMFO products.

Heavy Marine Fuel Composition

One aspect of the present inventive concept is a fuel compositioncomprising, but preferably consisting essentially of, the Product HMFOresulting from the processes disclosed, and may optionally includeDiluent Materials. The Product HMFO itself complies with ISO 8217 (2017)and meets the global IMO Annex VI requirements for maximum sulfurcontent (ISO 14596 or ISO 8754). If ultra-low levels of sulfur aredesired, the process of the present invention achieves this and one ofskill in the art of marine fuel blending will appreciate that a lowsulfur or ultra-low sulfur Product HMFO can be utilized as a primaryblending stock to form a global IMO Annex VI compliant low sulfur HeavyMarine Fuel Composition. Such a low sulfur Heavy Marine Fuel Compositionwill comprise (and preferably consist essentially of): a) the ProductHMFO and b) Diluent Materials. In one embodiment, the majority of thevolume of the Heavy Marine Fuel Composition is the Product HMFO with thebalance of materials being Diluent Materials. Preferably, the HeavyMaine Fuel Composition is at least 75% by volume, preferably at least80% by volume, more preferably at least 90% by volume, and furthermorepreferably at least 95% by volume Product HMFO with the balance beingDiluent Materials.

Diluent Materials may be hydrocarbon or non-hydrocarbon based materialsmixed into or combined with or added to, or solid particle materialssuspended in, the Product HMFO. The Diluent Materials may intentionallyor unintentionally alter the composition of the Product HMFO but not sothe resulting mixture violates the ISO 8217 (2017) standards forresidual marine fuels or fails to have a sulfur content lower than theglobal MARPOL standard of 0.5% wt. sulfur (ISO 14596 or ISO 8754).Examples of Diluent Materials considered hydrocarbon based materialsinclude: Feedstock HMFO (i.e. high sulfur HMFO); distillate based fuelssuch as road diesel, gas oil, MGO or MDO; cutter oil (which is used informulating residual marine fuel oils); renewable oils and fuels such asbiodiesel, methanol, ethanol, and the like; synthetic hydrocarbons andoils based on gas to liquids technology such as Fischer-Tropsch derivedoils, synthetic oils such as those based on polyethylene, polypropylene,dimer, trimer and poly butylene; refinery residues or other hydrocarbonoils such as atmospheric residue, vacuum residue, fluid catalyticcracker (FCC) slurry oil, FCC cycle oil, pyrolysis gasoil, cracked lightgas oil (CLGO), cracked heavy gas oil (CHGO), light cycle oil (LCO),heavy cycle oil (HCO), thermally cracked residue, coker heavydistillate, bitumen, de-asphalted heavy oil, visbreaker residue, slopoils, asphaltinic oils; used or recycled motor oils; lube oil aromaticextracts and crude oils such as heavy crude oil, distressed crude oilsand similar materials that might otherwise be sent to a hydrocracker ordiverted into the blending pool for a prior art high sulfur heavy(residual) marine fuel oil. Examples of Diluent Materials considerednon-hydrocarbon based materials include: residual water (i.e. waterabsorbed from the humidity in the air or water that is miscible orsolubilized, sometimes as microemulsions, into the hydrocarbons of theProduct HMFO), fuel additives which can include, but are not limited todetergents, viscosity modifiers, pour point depressants, lubricitymodifiers, de-hazers (e.g. alkoxylated phenol formaldehyde polymers),antifoaming agents (e.g. polyether modified polysiloxanes); ignitionimprovers; anti rust agents (e.g. succinic acid ester derivatives);corrosion inhibitors; anti-wear additives, anti-oxidants (e.g. phenoliccompounds and derivatives), coating agents and surface modifiers, metaldeactivators, static dissipating agents, ionic and nonionic surfactants,stabilizers, cosmetic colorants and odorants and mixtures of these. Athird group of Diluent Materials may include suspended solids or fineparticulate materials that are present because of the handling, storageand transport of the Product HMFO or the Heavy Marine Fuel Composition,including but not limited to: carbon or hydrocarbon solids (e.g. coke,graphitic solids, or micro-agglomerated asphaltenes), iron rust andother oxidative corrosion solids, fine bulk metal particles, paint orsurface coating particles, plastic or polymeric or elastomer or rubberparticles (e.g. resulting from the degradation of gaskets, valve parts,etc. . . . ), catalyst fines, ceramic or mineral particles, sand, clay,and other earthen particles, bacteria and other biologically generatedsolids, and mixtures of these that may be present as suspendedparticles, but otherwise don't detract from the merchantable quality ofthe Heavy Marine Fuel Composition as an ISO 8217 (2017) compliant heavy(residual) marine fuel.

The blend of Product HMFO and Diluent Materials must be of merchantablequality as a low sulfur heavy (residual) marine fuel. That is the blendmust be suitable for the intended use as heavy marine bunker fuel andgenerally be fungible and compatible as a bunker fuel for ocean goingships. Preferably the Heavy Marine Fuel Composition must retain the bulkphysical properties required of an ISO 8217 (2017) compliant residualmarine fuel oil and a sulfur content lower than the global MARPOLstandard of 0.5% wt. sulfur (ISO 14596 or ISO 8754) so that the materialqualifies as MARPOL Annex VI Low Sulfur Heavy Marine Fuel Oil (LS-HMFO).The sulfur content of the Product HMFO can be lower than 0.5% wt. (i.e.below 0.1% wt sulfur (ISO 14596 or ISO 8754)) to qualify as a MARPOLAnnex VI compliant Ultra-Low Sulfur Heavy Marine Fuel Oil (ULS-HMFO) anda Heavy Marine Fuel Composition likewise can be formulated to qualify asa MARPOL Annex VI compliant ULS-HMFO suitable for use as marine bunkerfuel in the ECA zones. To qualify as an ISO 8217 (2017) qualified fuel,the Heavy Marine Fuel Composition of the present invention must meetthose internationally accepted standards. The Bulk Properties of theHeavy Marine Fuel Composition should include: a maximum of kinematicviscosity at 50° C. (ISO 3104) between the range from 180 mm²/s to 700mm²/s; a density at 15° C. (ISO 3675) between the range of 991.0 kg/m³to 1010.0 kg/m³; a CCAI is in the range of 780 to 870; a flash point(ISO 2719) no lower than 60° C.; a total sediment—aged (ISO 10307-2)less than 0.10% wt.; and a carbon residue—micro method (ISO 10370) lessthan 20% wt., and an aluminum plus silicon (ISO 10478) content no morethan of 60 mg/kg.

Production Plant Description Production Plant Description:

Turning now to a more detailed illustrative embodiment of a productionplant, FIG. 2 shows a schematic for a production plant implementing theprocess described above for reducing the environmental contaminates in aFeedstock HMFO to produce a Product HMFO according to the secondillustrative embodiment. One of skill in the art will appreciate thatFIG. 2 is a generalized schematic drawing, and the exact layout andconfiguration of a plant will depend upon factors such as location,production capacity, environmental conditions (i.e. wind load, etc.) andother factors and elements that a skilled detailed engineering firm willbe able to provide. Such variations are contemplated and within thescope of the present disclosure.

In FIG. 2, Feedstock HMFO (A) is fed from outside the battery limits(OSBL) to the Oil Feed Surge Drum (1) that receives feed from outsidethe battery limits (OSBL) and provides surge volume adequate to ensuresmooth operation of the unit. Water entrained in the feed and bulksolids (sand, rust particles, etc.) are removed from the HMFO with thewater and bulk solids being discharged a stream (1 c) for treatmentOSBL.

The Feedstock HMFO (A) is withdrawn from the Oil Feed Surge Drum (1) vialine (lb) by the Oil Feed Pump (3) and is pressurized to a pressurerequired for the process. The pressurized HMFO (A′) then passes throughline (3 a) to the Oil Feed/Product Heat Exchanger (5) where thepressurized HMFO Feed (A′) is partially heated by the Product HMFO (B).The pressurized Feedstock HMFO (A′) passing through line (5 a) isfurther heated against the effluent from the Reactor System (E) in theReactor Feed/Effluent Heat Exchanger (7).

The heated and pressurized Feedstock HMFO (A″) in line (7 a) is thenmixed with Activating Gas (C) provided via line (23 c) at Mixing Point(X) to form a Feedstock Mixture (D). The mixing point (X) can be anywell know gas/liquid mixing system or entrainment mechanism well knownto one skilled in the art.

The Feedstock Mixture (D) passes through line (9 a) to the Reactor FeedFurnace (9) where the Feedstock Mixture (D) is heated to the specifiedprocess temperature. The Reactor Feed Furnace (9) may be a fired heaterfurnace or any other kind to type of heater as known to one of skill inthe art if it will raise the temperature of the Feedstock Mixture (D) tothe desired temperature for the process conditions.

The fully Heated Feedstock Mixture (D′) exits the Reactor Feed Furnace(9) via line 9 b and is fed into the Reactor System (11). The fullyheated Feedstock Mixture (D′) enters the Reactor System (11) whereenvironmental contaminates, such a sulfur, nitrogen, and metals arepreferentially removed from the Feedstock HMFO component of the fullyheated Feedstock Mixture. The Reactor System contains catalyst materialssome or all of which many be within a structured catalyst bed, and whichpreferentially removes the Environmental Contaminates, principallyorganometal and organosulfur compounds in the Feedstock HMFO componentby reacting them with hydrogen in the Activating Gas to form deposits ofmetals, metal sulfides and/or hydrogen sulfide. The Reactor System willalso achieve demetallization, denitrogenation, and a certain amount ofring opening hydrogenation of the complex aromatics and asphaltenes,however minimal hydrocracking of hydrocarbons should take place. Theprocess conditions of hydrogen partial pressure, reaction pressure,temperature and residence time as measured by liquid hourly velocity areoptimized to achieve desired final product quality. A more detaileddiscussion of the Reactor System, the structured catalyst beds, thecatalyst, the process conditions, and other aspects of the process arecontained below in the “Reactor System Description.”

The Reactor System Effluent (E) exits the Reactor System (11) via line(11 a) and exchanges heat against the pressurized and partially heatsthe Feedstock HMFO (A′) in the Reactor Feed/Effluent Exchanger (7). Thepartially cooled Reactor System Effluent (E′) then flows via line (11 c)to the Hot Separator (13).

The Hot Separator (13) separates the gaseous components of the ReactorSystem Effluent (F) which are directed to line (13 a) from the liquidcomponents of the Reactor System effluent (G) which are directed to line(13 b). The gaseous components of the Reactor System effluent in line(13 a) are cooled against air in the Hot Separator Vapor Air Cooler (15)and then flow via line (15 a) to the Cold Separator (17).

The Cold Separator (17) further separates any remaining gaseouscomponents from the liquid components in the cooled gaseous componentsof the Reactor System Effluent (F′). The gaseous components from theCold Separator (F″) are directed to line (17 a) and fed onto the AmineAbsorber (21). The Cold Separator (17) also separates any remaining ColdSeparator hydrocarbon liquids (H) in line (17 b) from any Cold Separatorcondensed liquid water (I). The Cold Separator condensed liquid water(I) is sent OSBL via line (17 c) for treatment.

The hydrocarbon liquid components of the Reactor System effluent fromthe Hot Separator (G) in line (13 b) and the Cold Separator hydrocarbonliquids (H) in line (17 b) are combined and are fed to the Oil ProductStripper System (19). The Oil Product Stripper System (19) removes anyresidual hydrogen and hydrogen sulfide from the Product HMFO (B) whichis discharged in line (19 b) to storage OSBL. The vent stream (M) fromthe Oil Product Stripper in line (19 a) may be sent to the fuel gassystem or to the flare system that are OSBL. A more detailed discussionof the Oil Product Stripper System is contained in the “Oil ProductStripper System Description.”

The gaseous components from the Cold Separator (F″) in line (17 a)contain a mixture of hydrogen, hydrogen sulfide and light hydrocarbons(mostly methane and ethane). This vapor stream (17 a) feeds an AmineAbsorber System (21) where it is contacted against Lean Amine (J)provided OSBL via line (21 a) to the Amine Absorber System (21) toremove hydrogen sulfide from the gases making up the Activating Gasrecycle stream (C′). Rich amine (K) which has absorbed hydrogen sulfideexits the bottom of the Amine Absorber System (21) and is sent OSBL vialine (21 b) for amine regeneration and sulfur recovery.

The Amine Absorber System overhead vapor in line (21 c) is preferablyrecycled to the process as a Recycle Activating Gas (C′) via the RecycleCompressor (23) and line (23 a) where it is mixed with the MakeupActivating Gas (C″) provided OSBL by line (23 b). This mixture ofRecycle Activating Gas (C′) and Makeup Activating Gas (C″) to form theActivating Gas (C) utilized in the process via line (23 c) as notedabove. A Scrubbed Purge Gas stream (H) is taken from the Amine AbsorberSystem overhead vapor line (21 c) and sent via line (21 d) to OSBL toprevent the buildup of light hydrocarbons or other non-condensablehydrocarbons. A more detailed discussion of the Amine Absorber System iscontained in the “Amine Absorber System Description.”

Reactor System Description:

The core process Reactor System (11) illustrated in FIG. 2 comprises asingle reactor vessel loaded with the process catalyst and sufficientcontrols, valves and sensors as one of skill in the art would readilyappreciate. One of skill in the art will appreciate that the reactorvessel itself must be engineered to withstand the pressures,temperatures and other conditions (i.e. presence of hydrogen andhydrogen sulfide) of the process. Using special alloys of stainlesssteel and other materials typical of such a unit are within the skill ofone in the art and well known. As illustrated, one or more beds in thereactor vessel may be a structured catalyst bed or a fixed dense packedcatalyst bed or combinations of these. A Reactor System containing atleast one reactor vessel with at least one structured catalyst bed ispreferred as these are easier to operate and maintain, however otherreactor types are also within the scope of the invention.

A description of the process catalyst, the selection of the processcatalyst and the grading of the catalyst within the reactor vessel iscontained in the “Catalyst in Reactor System”.

Alternative configurations for the core process Reactor System (11) arecontemplated. In one illustrative configuration, more than one reactorvessel may be utilized in parallel as shown in FIG. 3 to replace thecore process Reactor System (11) illustrated in FIG. 2.

In the embodiment shown in FIG. 3, each reactor vessel is loaded withprocess catalyst in a similar manner and each reactor vessel in theReactor System is provided the heated Feed Mixture (D′) via a commonline 9 b. The effluent from each reactor vessel in the Reactor System isrecombined and forms a combined Reactor Effluent (E) for furtherprocessing as described above via line 11 a. The illustrated arrangementwill allow the three reactors to carry out the process effectivelymultiplying the hydraulic capacity of the overall Reactor System.Control valves and isolation valves may also prevent feed from enteringone reactor vessel but not another reactor vessel. In this way onereactor can be by-passed and placed off-line for maintenance andreloading of catalyst while the remaining reactors continue to receiveheated Feedstock Mixture (D′). It will be appreciated by one of skill inthe art this arrangement of reactor vessels in parallel is not limitedin number to three, but multiple additional reactor vessels can be addedas shown by dashed line reactor. The only limitation to the number ofparallel reactor vessels is plot spacing and the ability to provideheated Feedstock Mixture (D′) to each active reactor.

A cascading series as shown in FIG. 4 can also be substituted for thesingle reactor vessel Reactor System 11 in FIG. 2. The cascading reactorvessels are loaded with process catalyst with the same or differentactivities toward metals, sulfur or other environmental contaminates tobe removed. For example, one reactor may be loaded with a highly activedemetallization catalyst, a second subsequent or downstream reactor maybe loaded with a balanced demetallization/desulfurizing catalyst, andreactor downstream from the second reactor may be loaded with a highlyactive desulfurization catalyst. This allows for greater control andbalance in process conditions (temperature, pressure, space flowvelocity, etc. . . . ) so it is tailored for each catalyst. In this wayone can optimize the parameters in each reactor depending upon thematerial being fed to that specific reactor/catalyst combination andminimize the hydrocracking reactions.

Another illustrative embodiment of the replacement of the single reactorvessel Reactor System 11 in FIG. 2 is a matrix of reactors composed ofinterconnected reactors in parallel and in series. A simple 2×2 matrixarrangement of reactors with associated control valves and pipingillustrates this embodiment, however a wide variety of matrixconfigurations such as 2×3; 3×3, etc. . . . are contemplated and withinthe scope of the present invention. A 2 reactor by 2 reactor (2×2)matrix of comprises four reactor vessels each with reactor inlet controlvalves and reactor outlet control valves associated with each vessel.Horizontal flow control valves regulate the flow across the matrix fromheated Feedstock (D′) in line 9 b to discharging Reactor Effluent (E)into line 11 a. Vertical flow control valves control the flow throughthe matrix from line 9 b to line 11 a. One of skill in the art willappreciate that control over the multiple valves and flow can beachieved using a computerized control system/distributed control system(DCS) or programmable logic controllers (PLC) programmed to work withautomatic motorized valve controls, position sensors, flow meters,thermocouples, etc. . . . . These systems are commercially availablefrom vendors such as Honeywell International, Schneider Electric; andABB. Such control systems will include lock-outs and other processsafety control systems to prevent opening of valves in manner that iseither not productive or unsafe.

One of skill in the art will quickly realize and appreciate that byopening and closing the valves and varying the catalyst loads present ineach reactor, a large number of configurations may be achieved. One suchconfiguration would be to open valves and close other valves such thatthe flow for heated Feed Mixture (D′) will pass through the reactors inseries. Another such configuration would be to open valves and closeother valves such that the flow of heated Feed Mixture (D′) will passthrough three of the reactors in series, but not the fourth. As with theprior example, the nature of the Feedstock HSFO and the catalyst loadedin each reactor and the presence or absence of structured catalyst bedsmay be optimized and adjusted to achieve the desired Product HSFOproperties, however for brevity of disclose all such variations will beapparent to one of skill in the art.

One of the benefits of having a multi-reactor Reactor System is that itallows for a reactor that is experiencing decreased activity or pluggingas a result of coke formation to be isolated and taken off line forturn-around (i.e. deactivated, catalyst and internals replaced, etc.)without the entire plant having to shut down. Another benefit as notedabove is that it allows one to vary the catalyst loading in the ReactorSystem so that the overall process can be optimized for a specificFeedstock HSFO. A further benefit is that one can design the piping,pumps, heaters/heat exchangers, etc. to have excess capacity so thatwhen an increase in capacity is desired, additional reactors can bequickly brought on-line. Conversely, it allows an operator to takecapacity off line, or turn down a plant output without having a concernabout turn down and minimum flow through a reactor. While the abovematrix Reactor System is described with reference to a fixed bed orpacked bed trickle flow reactor, one of skill in the art will appreciatethat other reactor types may be utilized. For example, one or more ofthe reactors may be configured to be ebullated bed up flow reactors orthree phase upflow bubble reactors, or counter-current reactors, orreactive distillation reactors the configuration of which will be knownto one of skill in the art. It is anticipated that many otheroperational and logistical benefits will be realized by one of skill inthe art from the Reactor Systems configurations disclosed.

Structured Catalyst Bed

Turning now to the structured catalyst bed, similar beds have beendisclosed in the prior art in relation to a variety of catalyst promotedreactions. See for example U.S. Pat. No. 4,731,229; U.S. Pat. No.5,073,236; U.S. Pat. No. 5,266,546; U.S. Pat. No. 5,431,890; U.S. Pat.No. 5,730,843; USUS2002068026; US20020038066; US20020068026;US20030012711; US20060065578; US20070209966; US20090188837;US2010063334; US2010228063; US20110214979; US20120048778; US20150166908;US20150275105; 20160074824; 20170101592 and US20170226433, the contentsof which are incorporated herein by reference. However all of thesedisclosures involve the product being distilled from heavier bottoms orfeedstock materials. For example heavy and light naphtha streams aredesulfurized with the desired light naphtha being the desired productfor the gasoline pool and the heavy naphtha either recycled or sent to aFCC unit for further upgrading. In contrast, the process of the currentinvention utilized the distillation separation process to removeundesired by-product hydrocarbons and gases produced by the catalyticreaction (i.e. ammonia and hydrogen sulfide) and the desired product isthe bottoms stream that is catalytically treated, but not distilled. Thestructured catalyst beds as described above are designed to balance thecatalyst density load, the catalyst activity load and the desired liquidspace velocity through the reactor so that an effective separation ordistillation of purified lighter products can be produced. As noted incontrast the present process functionally combines the functioning of areactor with a stripper column or knock down drum. A further problemthat will be solved by the structured catalyst bed is to reduce thepressure drop through the catalyst beds and provision of sufficientcontact of the Feedstock Mixture with the catalyst and mixing with theActivating Gas.

A first illustrative embodiment of the structured catalyst beds is shownin FIG. 5 and FIG. 6 in a side view. As illustrated in FIG. 5 is acatalyst retention composed of a pair of fluid permeable corrugatedmetal sheets (102 and 104), wherein the pair of the fluid permeablecorrugated metal sheets are aligned such that the corrugations aresinusoidal, have the same wave length and amplitude, but are out ofphase and thereby defining a catalyst rich space (106) and a catalystlean space (108). The catalyst rich space will be loaded with one ormore catalyst materials and optionally inert packing materials. Thecatalyst lean space (108) may be left empty or it may be loaded withinert packing such as ceramic beads, inactive (non-metal containing)catalyst support, glass beads, rings, wire or plastic balls and thelike. These inert packing materials may serve the role of assisting inthe mixing of the Activating Gas with the Feedstock HMFO, facilitate theremoval or separation of gaseous by products (i.e. hydrogen sulfide orammonia) from the process mixture or facilitate the separation of anyhydrocarbon by-products.

FIG. 6 shows in side perspective a plurality of catalyst retentionstructures (110, 112 and 114) formed into a structured catalyst bed(116). Structural supports (118) may be optionally incorporated into thestructured catalyst bed to lend rigidity as may be needed. As shown thecatalyst rich spaces are radially aligned such that the catalyst richspaces of one catalyst retention structure is aligned with the catalystrich structure of the adjacent layers. In the illustrated configuration,the radial angle between adjacent layers is 0° (or) 180°. One of skillin the art will appreciate that the angle of radial alignment betweenadjacent layers may be varied from 0° to 180°, preferably between 20°and 160° and more preferably 90° such that the catalyst rich areas inone layer are perpendicular to the adjacent layers. It will be furtherappreciated that the alignment of a particular set of three or morelayers need not be the same. Thus a first layer may be aligned along andthus define the 0° axis relative to the other two layers; a secondadjacent layer may be radially aligned along a 45° angle relative to thefirst layer; and the third layer aligned along a 90° angle relative tothe first layer. This pattern of alignment may be continued until thedesired number of layers is achieved. It also should be appreciated thatit may be desirable to angle of the catalyst rich spaces (ie. the planeof the catalyst retention structure), relative to the flow of FeedstockHMFO and Activating Gas within the reaction vessel. This relative angleis referred to herein as the inclination angle. As shown in FIG. 6, theinclination angel is perpendicular (90°) to the flow of Feedstock HMFOand Activating Gas through the reactor vessel. However, it will beappreciated that the inclination level may be varied between 0°, inwhich case the catalyst rich spaces are vertically aligned with the sidewalls of the reactor vessel and 90° in which case the catalyst richspaces are perpendicular to the side walls of the reactor vessel. Thusby varying both the radial alignment and the inclination angle of thecatalyst rich spaces, one will be able to achieve a wide variety andthus be able to optimize the flow of Feedstock HMFO though the reactorvessel with minimal plugging/coking.

A second illustrative embodiment of the structured catalyst beds isshown in FIG. 7 and FIG. 8 in a side view. As illustrated in FIG. 7,catalyst retention structure (200) is composed of a flat fluid permeablemetal sheet (202) and a corrugated fluid permeable metal sheet (204)aligned to be co-planar and thereby defining a catalyst rich space (206)and a catalyst lean space (208). As with the prior illustrativeembodiment, the catalyst rich space will contain one or more catalystmaterials and optionally inert packing materials and the catalyst leanspace will be empty or optionally contain inert packing materials. FIG. 8shows in side perspective a plurality of catalyst retention structures(210, 212 and 214) formed into a structured catalyst bed (216).Structural supports (218) may be optionally incorporated into thestructured catalyst bed to lend rigidity as may be needed. As shown thecatalyst rich spaces are radially aligned such that the catalyst richspaces of one catalyst retention structure is perpendicular with thecatalyst rich structure of the adjacent layers. In the illustratedconfiguration, the radial angle between adjacent layers is 90°. The sameconsiderations of radial alignment and inclination of the catalystretention structures described above will apply to this embodiment. Theprinciple benefit of the illustrated structured catalyst bed is that themanufacturing process because affixing the flat fluid permeable sheetand the corrugated fluid permeable sheet will be greatly simplified.Further as illustrated, if the corrugated sheet is constructed using 90°angle corrugations, each catalyst retention structure will be able towithstand much greater weight loadings than if the corrugations aresinusoidal.

The loading of the catalyst structures will depend upon the particlesize of the catalyst materials and the activity level of the catalyst.The structures should be loaded such that the open space will be atleast 10 volume % of the overall structural volume, and preferably willbe up to about 65% of the overall structural volume. Active catalystmaterials should be loaded in the catalyst support structure at a levelthat is dependent upon the catalyst activity level and the desired levelof treatment. For example a catalyst material that is highly active fordesulfurization may be loaded at a lower density than a less activedesulfurization catalyst material and yet still achieve the same overallbalance of catalyst activity per volume. One of skill in the art willappreciate that by systematically varying the amount of catalyst loadedper volume and the catalyst activity level one may optimize the activitylevel and fluid permeability levels of the structured catalyst bed. Inone such example, the catalyst density is such that over 50% of the openspace in the catalyst rich space, which in turn may occupy only have ofthe over space within the structured catalyst bed. In another examplecatalyst rich space is fully loaded (i.e. dense packed into eachcatalyst rich space), however the catalyst rich space may only occupy 30volume % of the overall structured catalyst bed. Thus it will beappreciated that the catalyst density in the catalyst rich space mayvary between 30 vol % and 100 vol % of the catalyst rich space. It willbe further appreciated that that catalyst rich space may occupy aslittle as 10 vol % of the overall structured catalyst bed or it mayoccupy as much as 80 vol % of the overall structured catalyst bed.

The liquid hourly space velocity within the structured catalyst bedsshould be between 0.05 oil/hour/m³ catalyst and 10.0 oil/hour/m³catalyst; preferably between 0.08 oil/hour/m³ catalyst and 5.0oil/hour/m³ catalyst and more preferably between 0.1 oil/hour/m³catalyst and 3.0 oil/hour/m³ catalyst to achieve deep desulfurizationusing a highly active desulfurization catalyst and this will achieve aproduct with sulfur levels below 0.1 ppmw. However, it will beappreciated by one of skill in the art that when there is lower catalystdensity, it may be desirable to adjust the space velocity to valueoutside of the values disclosed.

Catalyst in Reactor System:

Generally a reactor vessel in each Reactor System is loaded with one ormore process catalysts. The selection of the catalyst system in eachreactor vessel is a function of feedstock properties, productrequirements and operating constraints and optimization of the processcatalyst for the specific reactor and can be carried out by routinetrial and error by one of ordinary skill in the art.

Within the scope of the present invention, the process catalyst(s) (alsoreferred to as catalyst materials) comprise at least one metal selectedfrom the group consisting of the metals each belonging to the groups 6,8, 9 and 10 of the Periodic Table, and more preferably a mixedtransition metal catalyst such as Ni—Mo, Co—Mo, Ni—W or Ni—Co—Mo areutilized. The metal is preferably supported on a porous inorganic oxidecatalyst carrier. The porous inorganic oxide catalyst carrier is atleast one carrier selected from the group consisting of alumina,alumina/boria carrier, a carrier containing metal-containingaluminosilicate, alumina/phosphorus carrier, alumina/alkaline earthmetal compound carrier, alumina/titania carrier and alumina/zirconiacarrier. The preferred porous inorganic oxide catalyst carrier isalumina. The pore size and metal loadings on the carrier may besystematically varied and tested with the desired feedstock and processconditions to optimize the properties of the Product HMFO. One of skillin the art knows that demetallization using a transition metal catalyst(such a CoMo or NiMo) is favored by catalysts with a relatively largesurface pore diameter and desulfurization is favored by supports havinga relatively small pore diameter. Generally the surface area for thecatalyst material ranges from 200-300 m²/g. The systematic adjustment ofpore size and surface area, and transition metal loadings activities topreferentially form a demetallization catalyst or a desulfurizationcatalyst are well known and routine to one of skill in the art.

The catalyst selection utilized within and for loading the ReactorSystem may be preferentially designed with a catalyst loading schemethat results in the Feedstock Mixture first contacting a catalyst bedthat with a catalyst preferential to demetallization followed downstreamby a bed of catalyst with mixed activity for demetallization anddesulfurization followed downstream by a catalyst bed with highdesulfurization activity. Alternatively a bed of inert materials may beloaded as the first bed followed by a bed with high demetallizationactivity the two beds acting as a guard bed to minimize metal depositson the subsequent the desulfurization beds.

The objective of the Reactor System is to treat the Feedstock HMFO atthe severity required to meet the Product HMFO specification.Demetallization, denitrogenation and hydrocarbon hydrogenation reactionsmay also occur to some extent when the process conditions are optimizedso the performance of the Reactor System achieves the required level ofdesulfurization. Hydrocracking is preferably minimized to reduce thevolume of hydrocarbons formed as by-product hydrocarbons to the process.The objective of the process is to selectively remove the environmentalcontaminates from Feedstock HMFO and minimize the formation ofunnecessary by-product hydrocarbons (C₁-C₈ hydrocarbons).

The process conditions in each reactor vessel will depend upon thefeedstock, the catalyst utilized and the desired properties of theProduct HMFO. Variations in conditions are to be expected by one ofordinary skill in the art and these may be determined by pilot planttesting and systematic optimization of the process. With this in mind ithas been found that the operating pressure, the indicated operatingtemperature, the ratio of the Activating Gas to Feedstock HMFO, thepartial pressure of hydrogen in the Activating Gas and the spacevelocity all are important parameters to consider. The operatingpressure of the Reactor System should be in the range of 250 psig and3000 psig, preferably between 1000 psig and 2500 psig and morepreferably between 1500 psig and 2200 psig. The indicated operatingtemperature of the Reactor System should be 500° F. to 900° F.,preferably between 650° F. and 850° F. and more preferably between 680°F. and 800° F. The ratio of the quantity of the Activating Gas to thequantity of Feedstock HMFO should be in the range of 250 scf gas/bbl ofFeedstock HMFO to 10,000 scf gas/bbl of Feedstock HMFO, preferablybetween 2000 scf gas/bbl of Feedstock HMFO to 5000 scf gas/bbl ofFeedstock HMFO and more preferably between 2500 scf gas/bbl of FeedstockHMFO to 4500 scf gas/bbl of Feedstock HMFO. The Activating Gas should beselected from mixtures of nitrogen, hydrogen, carbon dioxide, gaseouswater, and methane, so Activating Gas has an ideal gas partial pressureof hydrogen (p_(H2)) greater than 80% of the total pressure of theActivating Gas mixture (P) and preferably wherein the Activating Gas hasan ideal gas partial pressure of hydrogen (p_(H2)) greater than 95% ofthe total pressure of the Activating Gas mixture (P). The Activating Gasmay have a hydrogen mole fraction in the range between 80% of the totalmoles of Activating Gas mixture and more preferably wherein theActivating Gas has a hydrogen mole fraction between 80% and 99% of thetotal moles of Activating Gas mixture. The liquid hourly space velocitywithin the Reactor System should be between 0.05 oil/hour/m³ catalystand 1.0 oil/hour/m³ catalyst; preferably between 0.08 oil/hour/m³catalyst and 0.5 oil/hour/m³ catalyst and more preferably between 0.1oil/hour/m³ catalyst and 0.3 oil/hour/m³ catalyst to achieve deepdesulfurization with product sulfur levels below 0.1 ppmw.

The hydraulic capacity rate of the Reactor System should be between 100bbl of Feedstock HMFO/day and 100,000 bbl of Feedstock HMFO/day,preferably between 1000 bbl of Feedstock HMFO/day and 60,000 bbl ofFeedstock HMFO/day, more preferably between 5,000 bbl of FeedstockHMFO/day and 45,000 bbl of Feedstock HMFO/day, and even more preferablybetween 10,000 bbl of Feedstock HMFO/day and 30,000 bbl of FeedstockHMFO/day. The desired hydraulic capacity may be achieved in a singlereactor vessel Reactor System or in a multiple reactor vessel ReactorSystem as described.

Modular Reactor

The Reactor System may be field constructed or modularized. Asignificant advantage of a modularized Reactor System will be theability to change-out entire reactor vessels; as opposed to changing outor revamping the internals of a conventional fixed in place reactor.When the active reactor must be shut down for servicing (i.e. changecatalyst, replace internals, etc. . . . ); the entire reactor (reactorvessel and internal components) may be changed out at rather thanconventionally changing out catalyst beds and internals on-site.Changing out of the reactor vessels will dramatically decrease timeplant down time by eliminating the on-site process of catalystunloading, loading and conditioning, minimize field construction/changeout activities, reduce safety risks and improve Plant operatingefficiency.

A modular Reactor System as contemplated by the present invention maycomprise a continuous tubular reactor vessel 102 defined by an outerwall surrounding an internal space. One or more inlet flanges 104 andone or more outlet flanges 106 flange are in fluid communication witheach other via the interior to the reactor vessel. The outer wall of thereactor vessel is sized so it will be contained within a standard ISO 20ft container (i.e. 2.43 m×2.59 m×6.06 m) or a standard ISO 40 ftcontainer (i.e. 2.43 m×2.59 m×12.2 m) framework structure 108. The outerwall of the reactor vessel will be supported and braced within the ISOcontainer framework in a conventional manner known to one of skill inthat art, but not shown in the drawing so that the framework and reactorvessel as a whole can be lifted and transported via truck or heavy cargovehicles. The one or more flanged inlets and outlets are sized andpositioned to accommodate the corresponding feedstock provision pipingand product outlet piping of the Plant. One or both of the reactorvessel head pieces can be flanged and removable using a suitably sizedhead flange 110. A removable reactor vessel head piece may be desirablebecause it may facilitate the loading and unloading of the internalstructures, including but not limited to trays, perforated supportplates, catalyst beds, structured catalyst beds, Raschig rings, Dixonrings, and combinations of these, at a location away from the activeplant (i.e. in a warehouse or other controlled environment). ModularReactor Systems such as the one described above contained within an ISO40 ft. container frame have been modeled in the process to have a nameplate capacity between 1600 bpd and 2400 bpd of HSFO. Thus when utilizedin combinations together in a matrix of reactors (as disclosed herein)expansion of capacity become simply a matter of having pre-designed thesupporting utilities (i.e. piping, pumps, controls, etc. to accommodatethe addition of new reactors to the Plant. For example, a set of threerectors set in series, the first reactor containing HDM catalystloading, the second reactor containing HDT catalyst loading and thethird reactor containing HDS catalyst loading, is expected to have anoverall throughput of approximately 2000 bpd. Doubling the capacity ofthe plant can be achieved by adding a second series of three reactors.In this way additional capacity can be quickly brought on-line or takeoff-line as needed.

To change out reactor vessels, the plant should be designed with acompliant safety zone around each modular reactor, so the plant cancontinue operations while the modular Reactor System to be replaced isbrought out of service and replaced with a second Modular ReactorSystem. Within the processes of the present invention, the modularReactor System to be changed out will be hydrocarbon freed, placed undernitrogen and passivated. Passivation may be by conventional means or itmay be with a material that will harden at ambient conditions to allowfor safely disconnecting and removal of the reactor vessel. A modularReactor System filled with preconditioned catalyst will replace theremoved reactor and conditioned and brought back on-line. Reactor vesselinternals, decommissioned catalyst and the like in the replaced modularReactor System can then be unloaded and recycled off-site or at alocation more suitable for such activities. Replacement internals,thermal couple replacement, insulation material patching or replacementand other services can be performed, and catalyst materials can beloaded in the revamped modular Reactor System, under controlledconditions of temperature and humidity (and if necessary under nitrogenor other inert atmosphere) into the modular Reactor System prior totransport back to the Plant site. The refurbished modular Reactor Systemmay be filled with a material that will harden at ambient conditions andmelt when heated to secure and protect the catalyst and vessel internalsduring transportation, which is described below in greater detail. Theencapsulation/solidification of the reactor internals will allow themodular Reactor System to be more easily transported via truck or railand lifted into position and reconnected at the plant. It will beappreciated by those skilled in the art that the flanges must be sealedoff with blind flange covers whenever the modular Reactor System istransported to and from the Plant or stored in reserve on-site. One ofskill in the art will appreciate that disconnecting, removal,replacement and reconnecting a modular Reactor System may be facilitatedby hydraulic lifts or platforms or frameworks designed to securelyreceive the modular Reactor System and then lift, reorient andappropriately align and reposition of the modular Reactor System to fitthe piping within the Plant. It is within the scope of this invention tohave a hydrotreating plant in which the primary hydrotreating reactorsare removable and replaceable with a modular Reactor System such as thatdescribed herein.

Hydrotreatment catalysts utilized in the modular Reactor Systemgenerally comprise an amorphous or crystalline oxide support such as analumina, a silica, a silica alumina, or a zeolite, on which at least oneelement from groups VIII and VI of the periodic table or a combinationof a plurality of elements from these same groups is deposited, forexample solids designated CoMo/Al₂O₃, NiMo/Al₂O₃ or NiW/Al₂O₃. They maybe sulfided in advance to endow them with catalytic performances forhydrocarbon hydroconversion reactions, and in particular hydrotreatmentsuch as hydrodesulfurization, and, demetallization) and certainhydrogenation reactions. This sulfurization step carried out prior tothe catalytic step can be carried out in two manners. In situsulfurization is characterized in that the catalyst in its oxide form isinitially charged into the hydrocarbon conversion reactor forsulfurizing. Ex situ pre-sulfurization, as described in U.S. Pat. Nos.4,719,195; 5,397,756; 7,582,587 incorporated by reference)pre-sulfurization of the catalyst is carried out in a location differentfrom the location in which the catalyst operates. One of skill in theart will appreciate that the catalyst can be pre-sulfided and passivatedex situ prior to loading into the transportable reactor, or after it hasbeen loaded to prevent self-heating which may lead to spontaneouscombustion. The processes of pre-sulfiding and passivation have beendescribed in the technical and patent literature, and are well known toone of skill in the art.

For this disclosure, the term “sulfided metal particles” refers to metaloxide particles converted to the sulfide form. Further, the term “metal(s)” includes metal oxide (s) in partially reduced form. The term“pre-sulfided catalyst (s)” refers to catalysts wherein part of themetals are in the oxide form, and part of the metals may have beenconverted to the sulfide form. Pre-sulfided catalysts typically containadditional sulfur compounds which facilitate the sulfiding of theremaining metal oxides during the startup process. The term“pre-sulfided catalyst (s)” refers to catalysts wherein the majority ofthe metal oxides have been converted to metal sulfides.

As part of the ex situ passivation and optional coating of a catalyst,the sulfided catalyst undergoes at least two treatments: controlledcontact with at least one surface active oxidizing agent (also calledthe passivation step), followed (optionally) by contact with at leastone coating agent with an initial melting point of over 100° C., whichcoats the surfaces of the catalyst (also called the coating step). Theword “coating” or “coated” does not rule out some reaction leading topassivation of the catalyst surfaces.

The passivation step involves the controlled contacting of thepre-sulfided catalyst with a surface active oxidizing agent, such asoxygen and/or an oxygen-containing hydrocarbon having at least 12 carbonatoms, for a sufficient time so a sulfurized catalyst is made lessspontaneously combustible.

When the first passivation step is a treatment in the presence of a gas(or gas stream) containing oxygen (for example deriving from dry ormoist air) which can advantageously be carried out at ambienttemperature. The reaction of oxygen adsorption onto the catalyst causesan exothermic effect preferably controlled so the temperature of theproduct remains below 50° C. One possibility is to control the partialpressures of oxygen admitted to the catalyst. Then, a preferred mannerof carrying out the invention is to initially treat the catalyst with agas at a partial pressure of less than 8 kPa of oxygen, and secondlywith a gas at a partial pressure of over 8 kPa of oxygen. It is alsopossible to carry out the oxidizing passivation process directly withone or more gas streams having a partial pressure of oxygen of over 8kPa. This first stage preferably ends when the exothermic effect has allbut disappeared (i.e. when the temperature of the solid no longerincreases or only increases slightly) or, if the operator has means forlimiting the temperature increase, the second stage of coating can thenbe started earlier.

When using an oxygen containing hydrocarbon in the first passivationstep, the contact temperature is greater than about 0° C. and typicallywill range from about 15° C. to about 350° C., preferably from about 20°C. to about 150° C. The contact temperature will vary depending on themelting point or sublimation temperature of the oxygen-containinghydrocarbon. For example, when the oxygen-containing hydrocarbon is asolid or a semi-solid such as lard, the oxygen-containing hydrocarbonprocess temperature should preferably be at least at a temperature ofthe melting point of the solid or semi-solid for a time sufficient forthe catalyst to flow freely (appear “dry” and not stick or clump). In aspecific example of lard as the oxygen-containing hydrocarbon, the lardis preferably contacted at a initial temperature of about 80° C. Theprocess temperature for contacting the oxygen-containing hydrocarbon andcatalyst can be readily determined by the melting point of the solid orsemi-solid at a given pressure environment or visually by checking ifthe oxygen-containing hydrocarbon flows. Contact times will depend ontemperature and the viscosity of the oxygen-containing hydrocarbon,higher temperatures requiring shorter times and higher viscosityrequiring longer times. Times will range from about 2 minutes to about 2hours, although longer contact times can also be used.

Preferably the oxygen-containing hydrocarbon is sufficiently flowable togive a sufficient contact with the catalyst. An oxygen-containinghydrocarbon which is liquid at the elevated temperature of contact ismore preferred for ease of handling. It is preferred that theoxygen-containing hydrocarbon is a higher hydrocarbon, i.e., one havinga carbon number greater than twelve, preferably greater than sixteen,more preferably greater than twenty. The upper carbon number of usefuloxygen-containing hydrocarbon is determined by the melting point,solidification point, or smoke point of this oxygen-containinghydrocarbon. While solid fatty oxygen-containing hydrocarbon havingcarbon numbers greater than 100 can be used, they are inconvenient sincethey must be heated to such a high temperature to be converted into aliquid, although they can be used with a solvent to put them in liquidform. Oxygen-containing hydrocarbons with carbon numbers within therange from about 12 to about 100, preferably from about 16 to about 80are found most useful.

The term “oxygen-containing hydrocarbon” refers to hydrocarbon moleculescontaining at least one oxygen atom, which includes, for example, acids,acid esters, alcohols, aldehydes, ketones and ethers. Theoxygen-containing hydrocarbon may be mixtures such as acid esters andalcohols, different acid esters and the like. The oxygen-containinghydrocarbon can be primary, secondary or tertiary. The hydrocarbonmoiety can be straight or branched chain carbon atom linkages, cyclic,acyclic or aromatic. The hydrocarbon moiety can further be saturated orunsaturated. Oxygen-containing hydrocarbons include, for example, higheralcohols having at least 12, preferably 16, more preferably 20 carbonatoms such as dodecanol, hexadecanol, farnesol, hexestrol, oleylalcohol, cetyl alcohol, hexacosanol, triacontanol, cocceryl alcohol andoctacosanol; higher ethers having at least 12, preferably 16, morepreferably 20 carbon atoms such as dicetyl ether; higher ketones havingat least 12 carbon atoms, preferably 16 carbon atoms, more preferably 20carbon atoms such as palmitone, 10-hydroxypalmitone and 3-octadecanone;higher aldehydes having at least 12 carbon atoms, preferably 16, morepreferably 20 carbon atoms such as palmitaldehyde and olealdehyde;higher acids having at least 12, preferably 16, more preferably 20carbon atoms such as saturated acids such as lauric, myristic, palmitic,stearic, and docosanoic acids for example, or unsaturated higher acidssuch as palmitoleic, oleic, linoleic, linolenic, eleostearic,ricinoleic, eicosenoic, docosenoic, eicosatetraenoic, eicosapentaenoic,decosapentaenoic and docosahexaenoic; higher acid esters having at least12, preferably 16, more preferably 20 carbon atoms including mono-, di-,tri- and poly-fatty acid esters including alkyl and aryl esters of theabove acids (e.g. benzyl oleate and butyl oleate) and esters of theabove acids with mono-glyceride, di-glycerides and triglycerides andmixtures thereof. These glyceride fatty acid esters having from 16 to100, more preferably 18 to 90, most preferably 20 to 80 carbon atoms arepreferred. Some examples of commercial glyceride fatty acid estersinclude soybean oil, linseed oil, safflower oil, corn oil, sunfloweroil, cottonseed oil, olive oil, tung oil, castor oil, rapeseed oil, talloil, peanut oil, coconut oil, palm oil, canbra oil, perilla oil, lard,tallow, marine fat or oil such as fish fat or oil (e.g. herring andsardine), vegetable residues and mixtures thereof. Some examples ofcommercial higher alcohols includes alkanol mixtures such as NEODOL™alcohols from Shell Chemical Company, including mixtures of C₉, C₁₀ andC₁₁ alkanols (NEODOL™ 91 Alcohol), mixtures of C₁₂ and C₁₃ alkanols(NEODOL™ 23 Alcohol), mixtures of C₁₂, C₁₃, C₁₄ and C₁₅ alkanols(NEODOL™ 25 Alcohol), and mixtures of C₁₄ and C₁₅ alkanols (NEODOL™ 45Alcohol); the ALFOL™ Alcohols from Vista Chemical Company, includingmixtures of C₁₀ and C₁₂ alkanols (ALFOL™ 1012 Alcohol), mixtures of C₁₂and C₁₄ alkanols (ALFOL™ 1214 Alcohol), mixtures of C₁₆ and C₁₈ alkanols(ALFOL™ 1618 Alcohol) and mixtures of C₁₆, C₁₈, and Cm alkanols (ALFOL™1620 Alcohol); the EPAL™ Alcohols from Ethyl Chemical Company, includingmixtures of Cm and C₁₂ alkanols (EPAL™ 1012 Alcohol), mixtures of C₁₂and C₁₄ alkanols (EPAL™ 1214 Alcohol) and mixtures of C₁₄, C₁₆, and Cisalkanols (EPAL™ 1418 Alcohol); and the TERGITOL-™ Alcohols from UnionCarbide Corporation, including mixtures of C₁₂, C₁₃, C₁₄ and C₁₅alkanols (TERGITOL-L™ 125 Alcohols). Suitable commercially availablealkanols prepared by the reduction of naturally occurring fatty acidesters includes for example, the CO and TA products of Procter andGamble Company and the TA alcohols of Ashland Oil Company. Higheroligomers and polymers of polyols such as alkylene glycols are alsosuitable as higher alcohols.

The optional coating treatment will involve the treatment of thepassivated catalyst material with a long chain waxy hydrocarbon orpolymer material to further protect the sulfided catalyst fromdeactivation. The coating agent should have a melting point no less thanthe maximum ambient air temperature (i.e. greater than about 60° C.) andmore preferably will have a melting point of over 80° C. to facilitatetransportation without premature melting. Waxy hydrocarbons should besufficiently hard (or crystalline) so the coated catalyst particles canbe formed into a solid mass. However not so hard that the solid massbecomes brittle or subject to cracking during transport. Waxes made fromhigher alkanes having a C₁₅-C₂₀ chain lengths should be sufficient, withsome limited branching. Waxes made from lipids or fatty acids or primaryor secondary long chain alcohols will also be useful. Long chainalcohols may also serve as the passivating agent disclosed above.Ideally, the wax material will have a melting point above 80° C., butlower than the lowest desired operating temperatures for the process(i.e. lower than 260° C.) to facilitate removal from the catalystmaterials. Generally upon exposure of the wax materials to elevatedtemperatures and a partial pressure of hydrogen, they are thermallyhydrocracked and rapidly removed from the active sulfided catalystmaterials. In an alternative embodiment, the coating material may bepolymeric, preferably a heat sensitive polymer such thermoplasticsexamples of which include polyethylene, polypropylene or poly butylene.One of skill in the art will appreciate that the chain length andstructure (iso-tactic v. syn-tactic v atactic) nature of the polymerchain will directly affect the properties and can be adjustedsystematically to obtain the desired properties.

In one embodiment of the invention, the passivation step is completed,and the catalyst will be sufficiently passivated for handling andloading of the catalyst under controlled conditions of temperature,oxygen content (i.e. under an oxygen depleted atmosphere such asnitrogen or argon) and humidity. In such instances, the passivated (butnot coated) catalyst will be loaded into the transportable reactor toform catalyst beds and/or will be loaded into the support structures ofthe pre-structured catalyst bed. This will allow the second step ofcoating to take place in the fully catalyst loaded transportable reactoritself or (with structured supports) the coating process will beperformed on the catalyst loaded structured supports outside of thetransportable reactor, so the coated catalyst loaded structured bedelements can be loaded into the transportable reactor.

Activation of the ex-situ pre-sulfided catalyst takes place in thetransportable reactor once the transportable reactor is connected to theprocess infrastructure. The activation step may involve heating thereactor first to a temperature to melt or liquify the coating materials.The heating step will be performed under inert atmosphere (such asnitrogen or argon) which might have a measurable partial pressure ofhydrogen. The heating step continues until the desired operatingconditions of temperature and pressure are reached. This may require theintroduction of a hydrocarbon (such as low sulfur diesel, marine gasoil, low sulfur residual materials in the presence of hydrogen andoptionally a hydrocarbon. This process of pre-conditioning the catalystand the transportable reactor prior to introducing Feedstock HMFOmaterial

Oil Product Stripper System Description:

The Oil Product Stripper System (19) comprises a stripper column (alsoknown as a distillation column or exchange column) and ancillaryequipment including internal elements and utilities required to removehydrogen, hydrogen sulfide and light hydrocarbons lighter than dieselfrom the Product HMFO. Such systems are well known to one of skill inthe art, see U.S. Pat. No. 6,640,161; U.S. Pat. No. 5,709,780; U.S. Pat.No. 5,755,933; U.S. Pat. No. 4,186,159; U.S. Pat. No. 3,314,879 U.S.Pat. No. 3,844,898; U.S. Pat. No. 4,681,661; or U.S. Pat. No. 3,619,377the contents of which are incorporated herein by reference, ageneralized functional description is provided herein. Liquid from theHot Separator (13) and Cold Separator (7) feed the Oil Product StripperColumn (19). Stripping of hydrogen and hydrogen sulfide and lighthydrocarbons lighter than diesel may be achieved via a reboiler, livesteam or other stripping medium. The Oil Product Stripper System (19)may be designed with an overhead system comprising an overheadcondenser, reflux drum and reflux pump or it may be designed without anoverhead system. The conditions of the Oil Product Stripper may beoptimized to control the bulk properties of the Product HMFO, morespecifically viscosity and density. It is also contemplated that asecond draw (not shown) may be included to withdraw a distillateproduct, preferably a middle to heavy distillate.

Amine Absorber System Description:

The Amine Absorber System (21) comprises a gas liquid contacting columnand ancillary equipment and utilities required to remove sour gas (i.e.hydrogen sulfide) from the Cold Separator vapor feed so the resultingscrubbed gas can be recycled and used as Activating Gas. Because suchsystems are well known to one of skill in the art, see U.S. Pat. No.4,425,317; U.S. Pat. No. 4,085,199; U.S. Pat. No. 4,080,424; U.S. Pat.No. 4,001,386; which are incorporated herein by reference, a generalizedfunctional description is provided herein. Vapors from the ColdSeparator (17) feed the contacting column/system (19). Lean Amine (orother suitable sour gas stripping fluids or systems) provided from OSBLis utilized to scrub the Cold Separator vapor so hydrogen sulfide iseffectively removed. The Amine Absorber System (19) may be designed witha gas drying system to remove the any water vapor entrained into theRecycle Activating Gas (C′). The absorbed hydrogen sulfide is processedusing conventional means OSBL in a tail gas treating unit, such as aClaus combustion sulfur recovery unit or sulfur recovery system thatgenerates sulfuric acid.

The following examples will provide one skilled in the art with a morespecific illustrative embodiment for conducting the process disclosedand claimed herein:

Example 1

Overview:

The purpose of a pilot test run is to demonstrate that feedstock HMFOcan be processed through a reactor loaded with commercially availablecatalysts at specified conditions to remove environmental contaminates,specifically sulfur and other contaminants from the HMFO to produce aproduct HMFO that is MARPOL compliant, that is production of a LowSulfur Heavy Marine Fuel Oil (LS—HMFO) or Ultra-Low Sulfur Heavy MarineFuel Oil (USL-HMFO).

Pilot Unit Set Up:

The pilot unit will be set up with two 434 cm³ reactors arranged inseries to process the feedstock HMFO. The lead reactor will be loadedwith a blend of a commercially available hydro-demetaling (HDM) catalystand a commercially available hydro-transition (HDT) catalyst. One ofskill in the art will appreciate that the HDT catalyst layer may beformed and optimized using a mixture of HDM and HDS catalysts combinedwith an inert material to achieve the desired intermediate/transitionactivity levels. The second reactor will be loaded with a blend of thecommercially available hydro-transition (HDT) and a commerciallyavailable hydrodesulfurization (HDS). Alternatively, one can load thesecond reactor simply with a commercially hydrodesulfurization (HDS)catalyst. One of skill in the art will appreciate that the specific feedproperties of the Feedstock HMFO may affect the proportion of HDM, HDTand HDS catalysts in the reactor system. A systematic process of testingdifferent combinations with the same feed will yield the optimizedcatalyst combination for any feedstock and reaction conditions. For thisexample, the first reactor will be loaded with ⅔ hydro-demetalingcatalyst and ⅓ hydro-transition catalyst. The second reactor will beloaded with all hydrodesulfurization catalyst. The catalysts in eachreactor will be mixed with glass beads (approximately 50% by volume) toimprove liquid distribution and better control reactor temperature. Forthis pilot test run, one should use these commercially availablecatalysts: HDM: Albemarle KFR 20 series or equivalent; HDT: AlbemarleKFR 30 series or equivalent; HDS: Albemarle KFR 50 or KFR 70 orequivalent. Once set up of the pilot unit is complete, the catalyst canbe activated by sulfiding the catalyst using dimethyldisulfide (DMDS) ina manner well known to one of skill in the art.

Pilot Unit Operation:

Upon completion of the activating step, the pilot unit will be ready toreceive the feedstock HMFO and Activating Gas feed. For the presentexample, the Activating Gas can be technical grade or better hydrogengas. The mixed Feedstock HMFO and Activating Gas will be provided to thepilot plant at rates and operating conditions as specified: Oil FeedRate: 108.5 ml/h (space velocity=0.25/h); Hydrogen/Oil Ratio: 570 Nm3/m3(3200 scf/bbl); Reactor Temperature: 372° C. (702° F.); Reactor OutletPressure: 13.8 MPa(g) (2000 psig).

One of skill in the art will know that the rates and conditions may besystematically adjusted and optimized depending upon feed properties toachieve the desired product requirements. The unit will be brought to asteady state for each condition and full samples taken so analyticaltests can be completed. Material balance for each condition should beclosed before moving to the next condition.

Expected impacts on the Feedstock HMFO properties are: Sulfur Content(wt %): Reduced by at least 80%; Metals Content (wt %): Reduced by atleast 80%; MCR/Asphaltene Content (wt %): Reduced by at least 30%;Nitrogen Content (wt %): Reduced by at least 20%; C1-Naphtha Yield (wt%): Not over 3.0% and preferably not over 1.0%.

Process conditions in the Pilot Unit can be systematically adjusted asper Table 4 to assess the impact of process conditions and optimize theperformance of the process for the specific catalyst and feedstock HMFOutilized.

TABLE 4 Optimization of Process Conditions HC Feed Rate (ml/h), Nm³H₂/m³ oil/ Temp Pressure Case [LHSV(/h)] scf H₂/bbl oil (° C./° F.)(MPa(g)/psig) Baseline 108.5 [0.25] 570/3200 372/702 13.8/2000 T1 108.5[0.25] 570/3200 362/684 13.8/2000 T2 108.5 [0.25] 570/3200 382/72013.8/2000 L1 130.2 [0.30] 570/3200 372/702 13.8/2000 L2  86.8 [0.20]570/3200 372/702 13.8/2000 H1 108.5 [0.25] 500/2810 372/702 13.8/2000 H2108.5 [0.25] 640/3590 372/702 13.8/2000 S1  65.1 [0.15] 620/3480 385/72515.2/2200

In this way, the conditions of the pilot unit can be optimized toachieve less than 0.5% wt. sulfur product HMFO and preferably a 0.1% wt.sulfur product HMFO. Conditions for producing ULS-HMFO (i.e. 0.1% wt.sulfur product HMFO) will be: Feedstock HMFO Feed Rate: 65.1 ml/h (spacevelocity=0.15/h); Hydrogen/Oil Ratio: 620 Nm³/m³ (3480 scf/bbl); ReactorTemperature: 385° C. (725° F.); Reactor Outlet Pressure: 15 MPa(g) (2200psig)

Table 5 summarizes the anticipated impacts on key properties of HMFO.

TABLE 5 Expected Impact of Process on Key Properties of HMFO PropertyMinimum Typical Maximum Sulfur Conversion/Removal 80% 90% 98% MetalsConversion/Removal 80% 90% 100%  MCR Reduction 30% 50% 70% AsphalteneReduction 30% 50% 70% Nitrogen Conversion 10% 30% 70% C1 through NaphthaYield 0.5%  1.0%  4.0%  Hydrogen Consumption (scf/bbl) 500 750 1500

Table 6 lists analytical tests to be carried out for thecharacterization of the Feedstock HMFO and Product HMFO. The analyticaltests include those required by ISO for the Feedstock HMFO and theproduct HMFO to qualify and trade in commerce as ISO compliant residualmarine fuels. The additional parameters are provided so that one skilledin the art will be able to understand and appreciate the effectivenessof the inventive process.

TABLE 6 Analytical Tests and Testing Procedures Sulfur Content ISO 8754or ISO 14596 or ASTM D4294 Density @ 15° C. ISO 3675 or ISO 12185Kinematic Viscosity @ 50° C. ISO 3104 Pour Point, ° C. ISO 3016 FlashPoint, ° C. ISO 2719 CCAI ISO 8217, ANNEX B Ash Content ISO 6245 TotalSediment - Aged ISO 10307-2 Micro Carbon Residue, mass % ISO 10370 H2S,mg/kg IP 570 Acid Number ASTM D664 Water ISO 3733 Specific ContaminantsIP 501 or IP 470 (unless indicated otherwise) Vanadium or ISO 14597Sodium Aluminum or ISO 10478 Silicon or ISO 10478 Calcium or IP 500 Zincor IP 500 Phosphorous IP 500 Nickle Iron Distillation ASTM D7169 C:HRatio ASTM D3178 SARA Analysis ASTM D2007 Asphaltenes, wt % ASTM D6560Total Nitrogen ASTM D5762 Vent Gas Component Analysis FID GasChromatography or comparable

Table 7 contains the Feedstock HMFO analytical test results and theProduct HMFO analytical test results expected from the inventive processthat indicate the production of a LS HMFO. It will be noted by one ofskill in the art that under the conditions, the levels of hydrocarboncracking will be minimized to levels substantially lower than 10%, morepreferably less than 5% and even more preferably less than 1% of thetotal mass balance.

TABLE 7 Analytical Results Feedstock HMFO Product HMFO Sulfur Content,mass % 3.0   0.3 Density @ 15 C., kg/m³ 990 950⁽¹⁾  Kinematic Viscosity@ 50 C., mm²/s 380 100⁽¹⁾  Pour Point, C. 20 10  Flash Point, C. 110100⁽¹⁾  CCAI 850 820  Ash Content, mass % 0.1   0.0 Total Sediment -Aged, mass % 0.1   0.0 Micro Carbon Residue, mass % 13.0   6.5 H2S,mg/kg 0 0 Acid Number, mg KO/g 1   0.5 Water, vol % 0.5 0 SpecificContaminants, mg/kg Vanadium 180 20  Sodium 30 1 Aluminum 10 1 Silicon30 3 Calcium 15 1 Zinc 7 1 Phosphorous 2 0 Nickle 40 5 Iron 20 2Distillation, ° C./° F. IBP 160/320 120/248  5% wt 235/455 225/437 10%wt 290/554 270/518 30% wt 410/770 370/698 50% wt  540/1004 470/878 70%wt  650/1202  580/1076 90% wt  735/1355  660/1220 FBP  820/1508 730/1346 C:H Ratio (ASTM D3178) 1.2   1.3 SARA Analysis Saturates 1622  Aromatics 50 50  Resins 28 25  Asphaltenes 6 3 Asphaltenes, wt % 6.0  2.5 Total Nitrogen, mg/kg 4000 3000   Note: ⁽¹⁾It is expected thatproperty will be adjusted to a higher value by post process removal oflight material via distillation or stripping from product HMFO.

The product HMFO produced by the inventive process will reach ULS HMFOlimits (i.e. 0.1% wt. sulfur product HMFO) by systematic variation ofthe process parameters, for example by a lower space velocity or byusing a Feedstock HMFO with a lower initial sulfur content.

Example 2: RMG-380 HMFO

Pilot Unit Set Up:

A pilot unit was set up as noted above in Example 1 with the followingchanges: the first reactor was loaded with: as the first (upper) layerencountered by the feedstock 70% vol Albemarle KFR 20 serieshydro-demetaling catalyst and 30% vol Albemarle KFR 30 serieshydro-transition catalyst as the second (lower) layer. The secondreactor was loaded with 20% Albemarle KFR 30 series hydrotransitioncatalyst as the first (upper) layer and 80% vol hydrodesulfurizationcatalyst as the second (lower) layer. The catalyst was activated bysulfiding the catalyst with dimethyldisulfide (DMDS) in a manner wellknown to one of skill in the art.

Pilot Unit Operation:

Upon completion of the activating step, the pilot unit was ready toreceive the feedstock HMFO and Activating Gas feed. The Activating Gaswas technical grade or better hydrogen gas. The Feedstock HMFO was acommercially available and merchantable ISO 8217 (2017) compliant HMFO,except for a high sulfur content (2.9 wt %). The mixed Feedstock HMFOand Activating Gas was provided to the pilot plant at rates andconditions as specified in Table 8 below. The conditions were varied tooptimize the level of sulfur in the product HMFO material.

TABLE 8 Process Conditions Product HC Feed Temp Pressure HMFO Rate(ml/h), Nm³ H₂/m³ oil/ (° C./ (MPa(g)/ Sulfur Case [LHSV(/h)] scf H₂/bbloil ° F.) psig) % wt. Baseline 108.5 [0.25] 570/3200 371/700 13.8/20000.24 T1 108.5 [0.25] 570/3200 362/684 13.8/2000 0.53 T2 108.5 [0.25]570/3200 382/720 13.8/2000 0.15 L1 130.2 [0.30] 570/3200 372/70213.8/2000 0.53 S1  65.1 [0.15] 620/3480 385/725 15.2/2200 0.10 P1 108.5[0.25] 570/3200 371/700    /1700 0.56 T2/P1 108.5 [0.25] 570/3200382/720    /1700 0.46

Analytical data for a representative sample of the feedstock HMFO andrepresentative samples of product HMFO are provided below:

TABLE 7 Analytical Results - HMFO (RMG-380) Feedstock Product ProductSulfur Content, mass % 2.9 0.3 0.1 Density @ 15° C., kg/m³ 988 932 927Kinematic Viscosity @ 382 74 47 50° C., mm²/s Pour Point, ° C. −3 −12−30 Flash Point, ° C. 116 96 90 CCAI 850 812 814 Ash Content, mass %0.05 0.0 0.0 Total Sediment - Aged, 0.04 0.0 0.0 mass % Micro CarbonResidue, 11.5 3.3 4.1 mass % H2S, mg/kg 0.6 0 0 Acid Number, mg KO/g 0.30.1 >0.05 Water, vol % 0 0.0 0.0 Specific Contaminants, mg/kg Vanadium138 15 <1 Sodium 25 5 2 Aluminum 21 2 <1 Silicon 16 3 1 Calcium 6 2 <1Zinc 5 <1 <1 Phosphorous <1 2 1 Nickle 33 23 2 Iron 24 8 1 Distillation,° C./° F. IBP 178/352 168/334 161/322 5% wt 258/496 235/455 230/446 10%wt 298/569 270/518 264/507 30% wt 395/743 360/680 351/664 50% wt 517/962461/862 439/822 70% wt  633/1172  572/1062  552/1026 90% wt  >720/>1328 694/1281  679/1254 FBP  >720/>1328  >720/>1328  >720/>1328 C:H Ratio(ASTM D3178) 1.2 1.3 1.3 SARA Analysis Saturates 25.2 28.4 29.4Aromatics 50.2 61.0 62.7 Resins 18.6 6.0 5.8 Asphaltenes 6.0 4.6 2.1Asphaltenes, wt % 6.0 4.6 2.1 Total Nitrogen, mg/kg 3300 1700 1600

As noted above in Table 7, both feedstock HMFO and product HMFOexhibited observed bulk properties consistent with ISO 8217 (2017) for amerchantable residual marine fuel oil, except that the sulfur content ofthe product HMFO was significantly reduced as noted above when comparedto the feedstock HMFO.

One of skill in the art will appreciate that the above product HMFOproduced by the inventive process has achieved not only an ISO 8217(2017) compliant LS HMFO (i.e. 0.5% wt. sulfur) but also an ISO 8217(2017) compliant ULS HMFO limits (i.e. 0.1% wt. sulfur) product HMFO.

Example 3: RMK-500 HMFO

The feedstock to the pilot reactor utilized in example 2 above waschanged to a commercially available and merchantable ISO 8217 (2017)RMK-500 compliant HMFO, except that it has high environmentalcontaminates (i.e. sulfur (3.3 wt %)). Other bulk characteristic of theRMK-500 feedstock high sulfur HMFO are provide below:

TABLE 8 Analytical Results - Feedstock HMFO (RMK-500) Sulfur Content,mass % 3.3 Density @ 15° C., kg/m³ 1006 Kinematic Viscosity @ 50° C.,mm²/s 500

The mixed Feedstock (RMK-500) HMFO and Activating Gas was provided tothe pilot plant at rates and conditions and the resulting sulfur levelsachieved in the table below

TABLE 9 Process Conditions HC Feed Rate Nm³ H₂/m³ Temp Pressure Product(ml/h), oil/scf (° C./ (MPa(g)/ (RMK-500) Case [LHSV(/h)] H₂/bbl oil °F.) psig) sulfur % wt. A 108.5 [0.25]  640/3600 377/710 13.8/2000 0.57 B95.5 [0.22] 640/3600 390/735 13.8/2000 0.41 C 95.5 [0.22] 640/3600390/735 11.7/1700 0.44 D 95.5 [0.22] 640/3600 393/740 10.3/1500 0.61 E95.5 [0.22] 640/3600 393/740 17.2/2500 0.37 F 95.5 [0.22] 640/3600393/740  8.3/1200 0.70 G 95.5 [0.22] 640/3600 416/780  8.3/1200

The resulting product (RMK-500) HMFO exhibited observed bulk propertiesconsistent with the feedstock (RMK-500) HMFO, except that the sulfurcontent was significantly reduced as noted in the above table.

One of skill in the art will appreciate that the above product HMFOproduced by the inventive process has achieved a LS HMFO (i.e. 0.5% wt.sulfur) product HMFO having bulk characteristics of a ISO 8217 (2017)compliant RMK-500 residual fuel oil. It will also be appreciated thatthe process can be successfully carried out under non-hydrocrackingconditions (i.e. lower temperature and pressure) that substantiallyreduce the hydrocracking of the feedstock material. It should be notedthat when conditions were increased to much higher pressure (Example E)a product with a lower sulfur content was achieved, however it wasobserved that there was an increase in light hydrocarbons and wildnaphtha production.

It will be appreciated by those skilled in the art that changes could bemade to the illustrative embodiments described above without departingfrom the broad inventive concepts thereof. It is understood, therefore,that the inventive concepts disclosed are not limited to theillustrative embodiments or examples disclosed, but it is intended tocover modifications within the scope of the inventive concepts asdefined by the claims.

1. A process for the production of a Product Heavy Marine Fuel Oil, theprocess comprising: mixing a quantity of Feedstock Heavy Marine Fuel Oilwith a quantity of Activating Gas mixture to give a Feedstock Mixture;contacting the Feedstock Mixture with one or more catalysts underreactive conditions to promote the formation of a Process Mixture fromsaid Feedstock Mixture, wherein said one or more catalysts are in theform of a structured catalyst bed; receiving said Process Mixture andseparating the liquid components of the Process Mixture from the bulkgaseous components of the Process Mixture; and separating any residualgaseous components and by-product hydrocarbon components from theProduct Heavy Marine Fuel Oil.
 2. The process of claim 1, wherein thestructured catalyst bed comprises a plurality of catalyst retentionstructures, each catalyst retention structure composed of a pair offluid permeable corrugated metal sheets, wherein the pair of the fluidpermeable corrugated metal sheets are aligned such that the corrugationsare out of phase and thereby defining a catalyst rich space and acatalyst lean space within the structured catalyst bed, wherein withinthe catalyst rich space there is one or more catalyst materials andoptionally inert packing materials.
 3. The process of claim 1, whereinthe structured catalyst bed contains one or more catalysts to promotethe transformation of the Feedstock mixture to a Process Mixture whereinthe structured catalyst bed comprises a plurality of catalyst retentionstructures, each catalyst retention structure composed of a pair offluid permeable corrugated metal sheets, wherein the pair of the fluidpermeable corrugated metal sheets are aligned such that the corrugationsare out of phase and thereby defining a catalyst rich space and acatalyst lean space within the structured catalyst bed, wherein withinthe catalyst rich space there is one or more catalyst materials andoptionally inert packing materials.
 4. The process of claim 1 whereinFeedstock Heavy Marine Fuel Oil complies with ISO 8217 (2017) and has asulfur content (ISO 14596 or ISO 8754) between the range of 5.0 mass %to 1.0 mass % and wherein the Product Heavy Marine Fuel Oil complieswith ISO 8217 (2017) and has a sulfur content (ISO 14596 or ISO 8754)between the range of 0.50 mass % to 0.05 mass %.
 5. The process of claim4, wherein said Feedstock Heavy Marine Fuel Oil has: a maximum ofkinematic viscosity at 50° C. (ISO 3104) between the range from 180mm²/s to 700 mm²/s; a maximum of density at 15° C. (ISO 3675) betweenthe range of 991.0 kg/m³ to 1010.0 kg/m³; a CCAI in the range of 780 to870; a flash point (ISO 2719) no lower than 60° C.; a totalsediment—aged (ISO 10307-2) of less than 0.10 mass %; a carbonresidue—micro method (ISO 10370) less than 20 mass %; and an aluminumplus silicon (ISO 10478) content less than 60 mg/kg.
 6. The process ofclaim 4, wherein said Product Heavy Marine Fuel Oil has: a maximum ofkinematic viscosity at 50° C. (ISO 3104) between the range from 180mm²/s to 700 mm²/s; a maximum of density at 15° C. (ISO 3675) betweenthe range of 991.0 kg/m³ to 1010.0 kg/m³; a CCAI in the range of 780 to870; a flash point (ISO 2719) no lower than 60° C.; a totalsediment—aged (ISO 10307-2) of less than 0.10 mass %; a carbonresidue—micro method (ISO 10370) less than 20 mass %; and an aluminumplus silicon (ISO 10478) content less than 60 mg/kg.
 7. The process ofclaim 1 wherein the catalyst materials comprises: a porous inorganicoxide catalyst carrier and a transition metal catalyst, wherein theporous inorganic oxide catalyst carrier is at least one carrier selectedfrom the group consisting of alumina, alumina/boria carrier, a carriercontaining metal-containing aluminosilicate, alumina/phosphorus carrier,alumina/alkaline earth metal compound carrier, alumina/titania carrierand alumina/zirconia carrier, and wherein the transition metal catalystis one or more metals selected from the group consisting of group 6, 8,9 and 10 of the Periodic Table; and wherein the Activating Gas isselected from mixtures of nitrogen, hydrogen, carbon dioxide, gaseouswater, and methane, such that Activating Gas has an ideal gas partialpressure of hydrogen (p_(H2)) greater than 80% of the total pressure ofthe Activating Gas mixture (P).
 8. The process of claim 1, wherein thereactive conditions comprise: the ratio of the quantity of theActivating Gas to the quantity of Feedstock Heavy Marine Fuel Oil is inthe range of 250 scf gas/bbl of Feedstock Heavy Marine Fuel Oil to10,000 scf gas/bbl of Feedstock Heavy Marine Fuel Oil; a the totalpressure is between of 250 psig and 3000 psig; and, the indicatedtemperature is between of 500° F. to 900° F., and, wherein the liquidhourly space velocity is between 0.05 oil/hour/m³ catalyst and 1.0oil/hour/m³ catalyst.
 9. A device for the production of a Product HeavyMarine Fuel Oil, the device comprising: means for mixing a quantity ofFeedstock Heavy Marine Fuel Oil with a quantity of Activating Gasmixture to give a Feedstock Mixture; means for heating the Feedstockmixture, wherein the means for mixing and means for heating are in fluidcommunication with each other; a Reaction System in fluid communicationwith the means for heating, wherein the Reaction System comprises one ormore reactor vessels wherein said reactor vessels contains one or morestructured catalyst bed containing one or more catalyst materials topromote the transformation of the Feedstock mixture to a ProcessMixture; means for receiving said Process Mixture and separating theliquid components of the Process Mixture from the bulk gaseouscomponents of the Process Mixture, said means for receiving in fluidcommunication with the reaction System; and means for separating anyresidual gaseous components and by-product hydrocarbon components fromthe Process Mixture to form a Product Heavy Marine Fuel Oil.
 10. Thedevice of claim 9, wherein Feedstock Heavy Marine Fuel Oil complies withISO 8217 (2017) and has a sulfur content (ISO 14596 or ISO 8754) betweenthe range of 5.0 mass % to 1.0 mass % and wherein the Product HeavyMarine Fuel Oil complies with ISO 8217 (2017) and has a sulfur content(ISO 14596 or ISO 8754) between the range of 0.50 mass % to 0.05 mass %.11. The device of claim 9, wherein the structured catalyst bed comprisesa plurality of catalyst retention structures, each catalyst retentionstructure composed of a pair of fluid permeable corrugated metal sheets,wherein the pair of the fluid permeable corrugated metal sheets arealigned such that the corrugations are out of phase and thereby defininga catalyst rich space and a catalyst lean space within the structuredcatalyst bed, wherein within the catalyst rich space there is one ormore catalyst materials and optionally inert packing materials andwherein the one or more catalyst materials is a porous inorganic oxidecatalyst carrier and a transition metal catalyst, wherein the porousinorganic oxide catalyst carrier is at least one carrier selected fromthe group consisting of alumina, alumina/boria carrier, a carriercontaining metal-containing aluminosilicate, alumina/phosphorus carrier,alumina/alkaline earth metal compound carrier, alumina/titania carrierand alumina/zirconia carrier, and wherein the transition metal catalystis one or more metals selected from the group consisting of group 6, 8,9 and 10 of the Periodic Table.
 12. The device of claim 11, wherein thecatalyst lean space contains inert packing materials.
 13. The device ofclaim 11, wherein two adjacent catalyst retention structures are alignedin parallel X-Y planes, but the catalyst rich spaces have an angle ofradial alignment greater than 0° and less than 180° in the X-Y plane.14. The device of claim 11, wherein the fluid permeable metal sheet isselected from the group consisting of: woven metal wire mesh, perforatedmetal plate; sintered porous metal plate, and combinations thereof. 15.The device of claim 9 wherein the structured catalyst bed comprises aplurality catalyst retention structures, wherein each catalyst retentionstructure is composed of a flat fluid permeable metal sheet and acorrugated fluid permeable metal sheet aligned to be co-planar andthereby defining a catalyst rich space and a catalyst lean space,wherein within the catalyst rich space there is one or more catalystmaterials and optionally inert packing materials and wherein the one ormore catalyst materials is a porous inorganic oxide catalyst carrier anda transition metal catalyst, wherein the porous inorganic oxide catalystcarrier is at least one carrier selected from the group consisting ofalumina, alumina/boria carrier, a carrier containing metal-containingaluminosilicate, alumina/phosphorus carrier, alumina/alkaline earthmetal compound carrier, alumina/titania carrier and alumina/zirconiacarrier, and wherein the transition metal catalyst is one or more metalsselected from the group consisting of group 6, 8, 9 and 10 of thePeriodic Table.
 16. The device of claim 15, wherein the catalyst leanspace contains inert packing materials.
 17. The device of claim 15,wherein two adjacent catalyst retention structures are aligned inparallel X-Y planes, but the catalyst rich spaces have an angle ofradial alignment greater than 0° and less than 180° in the X-Y plane.18. The device of claim 15, wherein the fluid permeable metal sheet isselected from the group consisting of: woven metal wire mesh, perforatedmetal plate; sintered porous metal plate, and combinations thereof. 19.The device of claim 15 wherein Feedstock Heavy Marine Fuel Oil complieswith ISO 8217 (2017) and has a sulfur content (ISO 14596 or ISO 8754)between the range of 5.0 mass % to 1.0 mass % and wherein the ProductHeavy Marine Fuel Oil complies with ISO 8217 (2017) and has a sulfurcontent (ISO 14596 or ISO 8754) between the range of 0.50 mass % to 0.05mass %.
 20. The device of claim 10 wherein Feedstock Heavy Marine FuelOil complies with ISO 8217 (2017) and has a sulfur content (ISO 14596 orISO 8754) between the range of 5.0 mass % to 1.0 mass % and wherein theProduct Heavy Marine Fuel Oil complies with ISO 8217 (2017) and has asulfur content (ISO 14596 or ISO 8754) between the range of 0.50 mass %to 0.05 mass %.